CN101868509B - Use of highly branched polymers in polymer dispersions for gloss colours - Google Patents

Use of highly branched polymers in polymer dispersions for gloss colours Download PDF

Info

Publication number
CN101868509B
CN101868509B CN200880116779.6A CN200880116779A CN101868509B CN 101868509 B CN101868509 B CN 101868509B CN 200880116779 A CN200880116779 A CN 200880116779A CN 101868509 B CN101868509 B CN 101868509B
Authority
CN
China
Prior art keywords
acid
weight
monomer
ester
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN200880116779.6A
Other languages
Chinese (zh)
Other versions
CN101868509A (en
Inventor
S·霍勒
B·布鲁赫曼
R·德尔施
D·舍恩菲尔德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN101868509A publication Critical patent/CN101868509A/en
Application granted granted Critical
Publication of CN101868509B publication Critical patent/CN101868509B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a method for producing coatings with increased gloss, aqueous coating agents for such a method, and the use of highly-branched polymers as additives for aqueous polymer dispersions for coating agents used to increase the gloss of coatings.

Description

Highly-branched polymers is for the polymeric dispersions of gloss colorant
The present invention relates to the method for coating that preparation has the glossiness of increase, relate to the water-borne coatings for described method, and relating to highly-branched polymers as the purposes of the additive of the aqueous polymer dispersions for coating, described coating produces the coating of the glossiness with increase.
Paint is divided three classes conventionally according to its reflecting power:
1. without wartwort, its mirror surface luster is that reflectivity is lower than 15%;
2. semi-gloss paint, its mirror surface luster is reflectivity approximately 35% to 50%; And
3. high lac varnish, its mirror surface luster is that reflectivity is greater than 70%;
Based on input angle, be the photometry of 60 ° separately.
Not pigmented coating based on aqueous polymer dispersions and the quality of specific pigmented coating depend primarily on the glossiness of gained coating.Therefore attempt improving glossiness by suitable additive always.Yet in many cases, these additives have and still demonstrate certain volatile shortcoming, this VOC to gained coating has detrimentally affect.
WO 00/29495 has described a kind of coating, and it comprises a kind of solvent, a kind of Synolac (vibrin) and a kind of star polymer.Described star polymer in described coating is as the properties-correcting agent that improves the performance of described coating, and the described performance of improving for example reaches lower viscosity.Described star polymer comes from the multi-functional thiol of containing at least three ethylenic unsaturated terminal chains.
WO 01/96411 has described a kind of amphiphilic star-like polymkeric substance with the core based on mercaptan, from described core, extends at least three polymeric arms, has also described described star polymer for the purposes of stabilized aqueous polymeric dispersions.
WO 2004/016700 has described a kind of water base copolymer dispersion, and it can obtain by using the branch-shape polymer of at least one alkenyl functional to carry out copolymerization.The remarkable part of gained copolymer dispersion is to have improved adhesion (blocking) character.The document is not instructed in hydrotropisms's polymeric dispersions and is added highly-branched polymers to provide water-borne coatings to make coating have the glossiness of increase.
WO 2004/016701 has described a kind of water-based homopolymer or copolymer dispersion, and it can obtain by letex polymerization, wherein uses a kind of branch-shape polymer of alkenyl functional as additive.Said composition can be used as the base-material of coating.There is no to disclose it for increasing the purposes of glossiness.
WO 2004/037928 has described a kind of air dried aqueous resin composition, its by a kind of can the lipid acid official of air drying can hyperbranched polymer, a kind of Non-amphiphilic Synolac, a kind of siccative and a kind of stablizer form.
WO 2005/003186 has described a kind of method of preparing aqueous polymer dispersions, described dispersion-based in the multipolymer that contains at least one hydrophobicity allyl group, vinyl, toxilic acid or diene monomers, be aggregated under the existence of at least one branch-shape polymer and carry out.Branch-shape polymer in this system makes even can use water solubility to carry out letex polymerization lower than the strong-hydrophobicity monomer of 0.001g/l.Do not record described branch-shape polymer as the additive of polymeric dispersions so that the water-borne coatings of the coating that can generate the glossiness with increase to be provided.
EP 1006165A2 has described a kind of coating composition that contains vinyl polymer, and described polymkeric substance has carbon siloxanes (carbosiloxane) dendrimers side group.These groups carry out free-radical polymerized being introduced into by the carbon siloxanes dendrimers with vinyl functional.This coating composition is for building industry, buildings, automobile etc.Coating is weather-proof, waterproof and freeze proof, and demonstrates good gloss retentivity and water repellency.
K.Manczyk, P.Szewczyk, at Prog.Org.Coat.2002, has described highly branched " high solid " Synolac in 44,99-109.These resins not only can be based on star structure but also can be based on dissaving structure.Along with the degree of branching increases, the dry quickening of these Synolac.Except other functions, also reported glossiness.But the document does not show that hyperbranched polymer is as for improving the suitability of the special additive of glossiness.One piece of similar disclosure is E.Bat, G.G ü nd ü z, and D.Kisak ü rek, and I.M.Akhmedoc is at Prog.Org.Coat.2006, the article in 55,330-336.
An object of the present invention is to provide for thering is the aqueous polymer dispersions of paint of the glossiness of increase.This dispersion especially should can be used for increasing the glossiness of the gloss paint based on acrylate dispersoid.
Surprisingly, find that this object used highly branched polymkeric substance to realize by the aqueous polymer dispersions for coating.
Therefore first the present invention provides by be coated with a kind of method that water-borne coatings is prepared the coating of the glossiness with increase on base material, and described water-borne coatings comprises a kind of aqueous polymer dispersions PD) and a kind of highly-branched polymers.
The present invention also provides the coating of waterborne compositions form, and it comprises:
-at least one is with undefined dispersion, and it comprises a kind of highly branched polymkeric substance as additive,
If-suitable, at least one mineral filler and/or mineral dye,
-conventional auxiliary agent, and
-add to the water of 100 % by weight.
The present invention also provides a kind of to be increased based on aqueous polymer dispersions PD by adding at least one highly-branched polymers) the method for glossiness of coating, described aqueous polymer dispersions can pass through at least one α, β-ethylenically unsaturated monomers M) free-radical emulsion polymerization obtain.
To polymeric dispersions PD) in add highly branched polymkeric substance can be at preparation PD) letex polymerization before and/or during and/or carry out afterwards.The interpolation of carrying out after letex polymerization also comprises the interpolation as a part for product configuration, and described product comprises a kind of based at least one α, β-ethylenically unsaturated monomers M) emulsion polymer.For this reason, at least one adds in paint as undefined highly branched polymkeric substance can be used as additive.The present invention therefore also provide at least one highly branched polymkeric substance as the additive of product to increase the purposes of the glossiness of coating prepared therefrom, described product comprise a kind of based at least one as undefined α, β-ethylenically unsaturated monomers M) emulsion polymer.
The present invention also provides as undefined highly branched polymkeric substance as the additive of water-borne coatings to increase the purposes of the glossiness of coating prepared therefrom, and described water-borne coatings comprises a kind of aqueous polymer dispersions PD).
The present invention also provides a kind of aqueous polymer dispersions PD) as the purposes of a kind of component in transparent varnish and high gloss paint, described aqueous polymer dispersions PD) comprise a kind of highly branched polymkeric substance as additive.
The glossiness of paint can be measured by DIN 67530.Paint is applied on sheet glass with the slit of wide 240 μ m and drying at room temperature 72 hours.Test sample is inserted to the reflexometer through calibration, use definite input angle, record reflection or scattering and the degree of back light.The reflexometer numerical value of measuring is measure (this value is higher, and glossiness is higher) of glossiness.
The glossiness of semi-gloss paint is preferably greater than 15 in the time of 60 °.The glossiness of the high lac varnish based on coating of the present invention is preferably greater than 60 in the time of 20 °.The glossiness of high lac varnish is preferably greater than 80 in the time of 60 °.
The polymeric dispersions PD using in the present invention) comprise preferably 0.1 to 15 % by weight, more preferably at least one highly branched polymkeric substance of 0.5 to 10 % by weight, the gross weight meter based on described polymeric dispersions.The usage quantity of described highly branched polymkeric substance is conventionally in the scope of for example 1 % by weight to 5 % by weight.
In the present invention, use highly-branched polymers to have advantages of that at least one is following:
Glossiness, the especially gloss paint based on acrylate dispersoid of-increase coating (paint),
-highly-branched polymers used and the highly compatible of multiple dispersion,
-avoid at least in part use to increase the additive of the VOC content of dispersion.
According to the present invention to polymeric dispersions PD) in add at least one highly-branched polymers.Phrase " highly-branched polymers " is often referred to the polymkeric substance that is characterized as highly branched structure and high functionality in the present invention.General Definition for highly-branched polymers, also can be referring to P.J.Flory, J.Am.Chem.Soc.1952,74,2718 and H.Frey et al., Chem.Eur.J.2000,6, No.14, the implication of 2499(when wherein they are mentioned is different with the definition of " hyperbranched polymer " selected herein).
Highly-branched polymers implication in the present invention comprises star polymer, dendrimers, dendrimer (arborol), and the highly-branched polymers that is different from these, for example hyperbranched polymer particularly.
Star polymer is the polymkeric substance that has three above chain Cong Yige centers to extend out.This center can be single atom or atomic group.
The structure of dendrimers derives from star polymer, but has carried out star-branched from every independent chain.By small molecules, the reaction sequence by continuous repetition obtains dendrimers, and described reaction sequence produces more branch, at the end of branch, has separately functional group, and described functional group is re-used as the starting point of further branching.Therefore the number of monomer end group is exponent increase with each reactions steps, finally forms tree structure, and it is spherical in the ideal situation.A feature of dendrimers is the number of reaction stages (algebraically) of carrying out during it synthesizes.Because dendrimers is constructed (in the ideal situation, the monomeric unit that all branches comprise identical number) uniformly, it is monodispersed substantially, and it has definite molar mass conventionally.
In molecule and structure, highly-branched polymers is below being called as dendrimers equally uniformly.
" hyperbranched polymer " in the context of the invention be different from above-mentioned dendrimers in molecule and structure inhomogeneous highly-branched polymers all.They have length and branching with and molar mass distribution on side chain and/or the side branch of difference (polymolecularity) to some extent.
The preferred per molecule of highly-branched polymers of the present invention has 10% to 100%, more preferably 10% to 90%, more especially 10% to 80% the per molecule degree of branching (DB).Degree of branching DB is defined as
DB (%)=(T+Z)/(T+Z+L) * 100, wherein
T is the mean number of the monomeric unit of end connection,
Z is the mean number of the monomeric unit of formation branch,
L is the mean number of the monomeric unit of straight chain connection.
Dendrimers has at least 99% conventionally, 99.9% to 100% degree of branching DB especially.
Hyperbranched polymer preferably has 10% to 95%, more preferably 25% to 90%, 30% to 80% degree of branching DB more especially.
In order to obtain favourable gloss character, not only can use uniform dendrimers on structure and molecule, can also use hyperbranched polymer.But the preparation of hyperbranched polymer is conventionally easier and more economical than dendrimers.Therefore; for example the preparation of single dispersion dendrimers is more complicated; this is because in each Connection Step; need to introduce blocking group again by its removal; and before each new growth phase starts; need to carry out a large amount of washing operations, reason that why dendrimers can only be prepared in laboratory scale conventionally that Here it is.The molecular weight distribution of hyperbranched polymer also can produce Beneficial Effect to carry out the viscometric properties of the dispersion of modification with it.Hyperbranched polymer also has more flexible structure than dendrimers.
The material that is suitable as highly-branched polymers is those materials that can obtain by polycondensation, addition polymerization or the addition polymerization of ethylenically unsaturated compounds normally.Preferred polycondensate.Polycondensation means the repetition chemical reaction that functional compound and suitable reactive compounds carry out, and cancellation low-molecular weight compound such as water, ethanol, HCl etc.Addition polymerization means repetition chemical reaction that functional compound and suitable reactive compounds carry out and not cancellation low-molecular weight compound.
The polymkeric substance that applicable use contains the functional group that is preferably selected from following group: ether, ester group, carbonate group, amino, amide group, carbamate groups and urea groups.
As polymkeric substance, can use polycarbonate, polyester, polyethers, polyurethane(s), polyureas, polyamine and polymeric amide more especially, with and hybrid form, such as poly-(Semicarbazido manthanoate), poly-(ether amine), poly-(ester amine), poly-(ether acid amides), poly-(esteramides), poly-(amide amine), poly-(ester carbonic ether), poly-(ether carbonate), poly-(ether-ether), poly-(ether-ether carbonic ether) etc.
Preferred hyperbranched polymer is the hyperbranched polymer based on ether, amine, ester, carbonic ether, acid amides and their hybrid form such as esteramides, amide amine, ester carbonic ether, ether carbonate, ether-ether, ether-ether carbonic ether, Semicarbazido manthanoate etc.
As hyperbranched polymer, can use more especially hyperbranched polycarbonates, hyperbranched poly (ether carbonate), hyperbranched poly (ether-ether), hyperbranched poly (ether-ether carbonic ether), hyper-branched polyester, hyperbranched polyether, hyperbranched poly carbamate, hyperbranched poly (Semicarbazido manthanoate), hyperbranched polyureas, hyperbranched polyamine, ultrabranching polyamide, hyperbranched poly (ether amine), hyperbranched poly (ester amine), hyperbranched poly (ether acid amides), hyperbranched poly (esteramides), and the mixture of these materials.A kind of hyperbranched polymer of particular form is hyperbranched polycarbonates.The hyperbranched polymer of another kind of particular form is the hyperbranched polymer of nitrogen atom, especially polyurethane(s), polyureas, polyamine, polymeric amide, poly-(esteramides) and poly-(ester amine).
As highly-branched polymers, preferably use hyperbranched polycarbonates, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether), or the mixture of the hyperbranched polymer that contains at least one hyperbranched polycarbonates, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether).
The hyperbranched polymer that the present invention be applicable to use with and preparation method thereof in Publication about Document, be described, these documents are all included the application by reference in.
Highly branched, the especially hyperbranched polycarbonate of-WO 2005/026234,
The hyper-branched polyester of-WO 01/46296, DE 10163163, DE 10219508 or DE 10240817,
The hyperbranched polyether of-WO 03/062306, WO 00/56802, DE 10211664 or DE 19947631,
The hyperbranched polymer of the nitrogen atom that-WO 2006/087227 records (especially polyurethane(s), polyureas, polymeric amide, poly-(esteramides), poly-(ester amine)),
The hyperbranched poly carbamate of-WO 97/02304 or DE 19904444,
The hyperbranched poly of-WO 97/02304 or DE 19904444 (Semicarbazido manthanoate),
The hyperbranched polyureas that-WO 03/066702, WO 2005/044897 and WO 2005/075541 record,
The hyperbranched amido polymer of-WO 2005/007726, especially poly-(ester amine),
The hyperbranched poly of-WO 99/16810 or EP 1036106 (esteramides),
The ultrabranching polyamide that-WO 2006/018125 records,
The hyperbranched poly (ester carbonic ether) that-WO 2006/089940 records.
Preferred polymkeric substance is weight-average molecular weight M wapproximately 500 to 500000, preferably 750 to 200000, be more particularly 1000 to 100000 polymkeric substance.Molecular weight can by gel permeation chromatography with standard substance for example polymethylmethacrylate measure.
In the context of the invention, statement " alkyl " comprises straight chain and branched alkyl group.Suitable short-chain alkyl group is for example straight or branched C 1-C 7alkyl, preferably C 1-C 6alkyl, more preferably C 1-C 4alkyl.It is more particularly including methyl, ethyl, propyl group, sec.-propyl, normal-butyl, 2-butyl, sec-butyl, the tertiary butyl, n-pentyl, 2-amyl group, 2-methyl butyl, 3-methyl butyl, 1, 2-dimethyl propyl, 1, 1-dimethyl propyl, 2, 2-dimethyl propyl, 1-ethyl propyl, n-hexyl, 2-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 3-dimethylbutyl, 1, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3, 3-dimethylbutyl, 1, 1, 2-trimethylammonium propyl group, 1, 2, 2-trimethylammonium propyl group, 1-ethyl-butyl, 2-ethyl-butyl, 1-Ethyl-2-Methyl propyl group, n-heptyl, 2-heptyl, 3-heptyl, 2-ethyl pentyl group, 1-propyl group butyl etc.
Suitable long-chain C 8-C 30alkyl is straight or branched alkyl.It is preferably the alkyl group of substantially linear, and such alkyl group is also present in natural or synthetic fatty acid and fatty alcohol and oxo alcohol (oxo-process alcohol).It is such as comprising n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base etc.Statement " alkyl " comprises unsubstituted and substituted alkyl group.
The explanation of abovementioned alkyl is also applicable to the moieties of arylalkyl.Preferred aromatic yl alkyl group is phenmethyl and styroyl.
In the context of the invention, C 8-C 32thiazolinyl represents straight chain and branched-chain alkenyl, and it can be cholesterol, two unsaturated or polyunsaturated.Preferred C 10-C 20thiazolinyl.Statement " thiazolinyl " comprises unsubstituted and substituted alkenyl group.Described group is the alkenyl group of substantially linear especially, and such alkenyl group is also present in natural or synthetic fatty acid and fatty alcohol and oxo alcohol.It is more particularly including octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base, vaccenic acid base, 19 carbene bases, sub-oil base (linolyl), flax base (linolenyl), 9,11,13-, 18 carbon trialkenyl and oil base (9-vaccenic acid base).
Statement " alkylidene group " represents to have the straight or branched alkane two base groups of 1 to 7 carbon atom, such as methylene radical, ethylene, trimethylene etc. in the present invention.
Cycloalkyl preferably represents C 4-C 8cycloalkyl, for example cyclobutyl, cyclopentyl, cyclohexyl, suberyl or ring octyl group.
Statement " aryl " comprises monocycle or polynuclear aromatics base in the present invention, and it can not be substituted or be substituted.Statement " aryl " preferably represent phenyl, tolyl, xylyl, base, duryl, naphthyl, fluorenyl, anthryl, phenanthryl or naphthyl, more preferably phenyl or naphthyl, these aryl conventionally can be with 1,2,3,4 or 5, preferred 1,2 or 3 substituting group in substituted situation.
More be particularly suitable for for the synthetic hyperbranched polymer that is applicable to the inventive method for being called as AB xthe material of monomer.These monomers have two kinds of different functional group A and B, and this functional group can react to each other to form and connect.A functional group only exists one in each molecule, and B functional group exists two or more (AB for example 2or AB 3monomer).AB xmonomer can side chain form included in hyperbranched polymer completely; It can be included into as end group, and therefore still has x free B group; It also can be used as the linear group with (x-1) individual free group and is included into.According to the polymerization degree, the hyperbranched polymer obtaining has more or less B group, and described B group is positioned at end or as side group.Further details is referring to for example Journal of Molecular Science, Rev.Macromol.Chem.Phys., C37 (3), 555-579 (1997).
For example, except the group of acquisition in dissaving structure synthetic (carbonate group during synthesis of super branched polycarbonate; Carbamate during synthesis of super branched polyurethane(s) and/or urea groups, and other groups that obtained by the reaction of isocyanate groups; Amide groups during synthesis of super branched polymeric amide etc.), outside, the hyperbranched polymer that the present invention uses preferably also contains at least four other functional groups.The maximum number of these functional groups is conventionally inessential.But under many circumstances, it is no more than 100.The number of functional group is preferably 4 to 100, and especially 5 to 80, more particularly 6 to 50.
For example be independently from each other-OC of other functional end-groups (=O) OR ,-COOH ,-COOR ,-CONH in the hyperbranched polymer that the present invention uses 2,-CONHR ,-OH ,-NH 2,-NHR and-SO 3h.End is that the hyperbranched polymer of OH, COOH and/or ROC (=O) O-group is proved to be advantageous particularly.
Hyperbranched polycarbonates
The hyperbranched polycarbonates that is applicable to increase glossiness can be prepared by for example following steps:
A) making at least one general formula is R aoC (=O) OR borganic carbonate (A) react with at least one fatty alcohol that contains at least 3 OH groups (B), and cancellation alcohol R aoH and R boH, obtains one or more condensation products (K), R aand R bbe selected from independently of one another straight or branched alkyl, arylalkyl, cycloalkyl and aromatic yl group, R aand R btogether with group-OC (=O) O-that also can connect with them as cyclic carbonate,
B) condensation product (K) carries out the hyperbranched polycarbonates that intermolecular reaction generates high functionality,
In reaction mixture, the ratio of OH group and carbonic ether is selected as making condensation product (K) on average to contain a carbonate group and more than one OH group, or contains an OH group and more than one carbonate group.Radicals R aand R bcan there is identical or different definition.In a concrete scheme, R aand R bthere is identical definition.Preferred R aand R bbe selected from C 1-C 20alkyl, C 5-C 7cycloalkyl, C 6-C 10aryl and C 6-C 10aryl-C 1-C 20alkyl, as defined above.R aand R balso can be together C 2-C 6alkylidene group.R particularly preferably aand R bbe selected from the C of straight chain and side chain 1-C 5alkyl, as above definition.
Dialkyl carbonate or diaryl carbonate can be by for example fatty alcohol, fragrant fatty alcohol (araliphatic alcohol) or aromatic alcohol, the preferably preparations of reacting of monohydroxy-alcohol and phosgene.In addition, it also can pass through alcohol or phenol at precious metal, oxygen or NO xexistence under by CO oxidative carbonylation, prepared.About the preparation method of diaryl carbonate or dialkyl carbonate, also can be referring to Ullmann ' s Encyclopedia of Industrial Chemistry, 6 thedition, 2000Electronic Release, Wiley-VCH.
The example of suitable carbonic ether comprises aliphatics or aromatic carbonate, ethylene carbonate, 1 for example, the two dodecyl esters of 2-Texacar PC or 1,3-Texacar PC, diphenyl carbonate, carboxylol ester, carbonic acid bis-xylene ester, carbonic acid dinaphthyl ester, carbonic acid ethyl phenyl ester, dimethyl benzyl, methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, carbonic acid diisobutyl ester, diamyl carbonate, carbonic acid dihexyl, carbonic acid two cyclohexyls, carbonic acid two heptyl esters, carbonic acid dioctyl ester, carbonic acid didecyl ester and carbonic acid.
Preferably use aliphatic acid ester carbonate, more especially in group, contain the aliphatic acid ester carbonate of 1 to 5 C atom, for example methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or carbonic acid diisobutyl ester.
Organic carbonate and at least one fatty alcohol that contains at least 3 OH groups (B) or with the mixture reaction of two or more different alcohol.
The example with the compound of at least three OH groups is glycerol, Pehanorm, trimethylolethane, TriMethylolPropane(TMP), 1,2,4-trihydroxybutane, three (methylol) amine, triethanolamine, tripropanolamine, tetramethylolmethane, two (TriMethylolPropane(TMP)s), two (tetramethylolmethanes), Glycerol dimer, triglycerin or low Polyglycerine, or be for example glucose of sugar, have three or high functionality and based on having three or the more alcohol of high functionality and the Aethoxy Sklerol of oxyethane, propylene oxide or butylene oxide ring more, or polyesterols.Particularly preferably glycerol, trimethylolethane, TriMethylolPropane(TMP), BT, tetramethylolmethane, with and Aethoxy Sklerol based on oxyethane or propylene oxide.
These polyfunctional alcohols also can be used in the mixture of difunctional alcohol (B '), and condition is that the average OH functionality of all alcohol used is higher than 2.The example with the suitable compound of two OH groups comprises ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol and 1, ammediol, dipropylene glycol, tripropylene glycol, neopentyl alcohol, 1,2-butyleneglycol, 1,3 butylene glycol and BDO, 1,2-pentanediol, 1,3-pentanediol and 1,5-PD, hexylene glycol, ring pentanediol, cyclohexanediol, cyclohexanedimethanol, and dual functional Aethoxy Sklerol or polyesterols.
Carbonic ether reacts with alcohol or alcohol mixture by the alcohol of cancellation simple function from carbonic ether molecule or phenol and generates for high functionality hyperbranched polycarbonates of the present invention.
The high functionality hyperbranched polycarbonates generating by described method with hydroxyl and/or carbonate group end-blocking, does not carry out further modification after this reaction.It can easily be dissolved in multi-solvents, water for example, and alcohol is as methyl alcohol, ethanol, butanols, alcohol/water mixture, acetone, 2-butanone, ethyl acetate, butylacetate, acetic acid methoxyl group propyl ester, acetic acid methoxyl group ethyl ester, tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, ethylene carbonate or Texacar PC.
High functionality polycarbonate means also to contain at least four, the preferred at least product of Ba Ge functional group endways or on side chain except the carbonate group of formation polymer backbone in the context of the invention.Described functional group is carbonate group and/or OH group.Conventionally, the number of end or side chain functionalities does not have the upper limit; But the product with very many functional groups may demonstrate undesired character, for example high viscosity or low solubility.High functionality polycarbonate of the present invention conventionally has and is no more than 500 ends or side chain functionalities, is preferably no more than 100, is more especially no more than 50 ends or side chain functionalities.
For preparing described high functionality polycarbonate, must will be set as making the simplest condensation product (hereinafter referred to condensation product (K)) of gained on average contain a carbonate group and more than one OH group or contain an OH group and more than one carbonate group containing the compound of OH and the ratio of carbonic ether.The simple structure of the condensation product (K) of carbonic ether (A) and glycol or polyvalent alcohol (B) is for arranging XY nor YX n, X is carbonate group, and Y is hydroxyl, and n is generally 1 to 6, preferably 1 to 4, more preferably 1 to 3 integer.Reactive group is generated as separate base, hereinafter referred to as " focus group ".
For example, when by carbonic ether and the dibasic alcohol the simplest condensation product of preparation (K), reaction ratio is 1:1, obtains the molecule of average out to XY type.When preparing condensation product (K) by carbonic ether and trivalent alcohol with the reaction ratio of 1:1, obtain average out to XY 2the molecule of type.When preparing condensation product (K) with the reaction ratio of 1:1 equally by carbonic ether and tetravalent alcohol, obtain average out to XY 3the molecule of type.Condensation product (K) also can for example be prepared with the reaction ratio of mol ratio 2:1 by carbonic ether and trivalent alcohol.Now obtain average out to X 2the molecule of Y type, focus group is herein OH group.When for example two carbonic ethers of glycol add in component by difunctional compound in addition, cause chain extension.The same average out to XY that obtains 2the molecule of type, focus group is carbonate group.According to the present invention, simple condensation product (K) carries out intermolecular reaction and forms high functionality polycondensation product (P).The reaction that generates condensation product (K) and polycondensation product (P) conventionally 0 to 250 ℃, preferably at the temperature of 60 to 160 ℃, in body or solution, occur.In this case, any solvent that conventionally can to use each reactant be inertia.Preferably with an organic solvent, for example decane, dodecane, benzene, toluene, chlorobenzene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE or solvent naphtha.
In a preferred embodiment, described condensation reaction is carried out in body.Can from molecular balance, remove the simple function alcohol roh or the phenol that in reaction, discharge, to add fast response, this removes by distillation mode and is undertaken, if be suitably under the pressure of reduction, carries out.
If use distillation to remove, conventionally preferably use and emit boiling point lower than the carbonic ether of the alcohol roh of 140 ℃ in reaction.
In order to add fast response, can also add catalyzer or catalyst mixture.Suitable catalyzer is the compound of catalytic esterification or transesterification reaction, for example alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate, the above-claimed cpd of preferred sodium, potassium or caesium, tertiary amine, guanidine, ammonium compound phosphonium compounds, organoaluminum, organotin, organic zinc, organic titanium, organic zirconium or bismuth organic compound, and the catalyzer that is known as double metal cyanide (DMC) class catalyzer, described in for example DE 10138216 or DE 10147712.
Preferably use potassium hydroxide, salt of wormwood, saleratus, diazabicyclo octane (DABCO), diazabicyclo-nonene (DBN), diazabicyclo undecylene (DBU), imidazoles is imidazoles, 1-Methylimidazole or 1,2 dimethylimidazole for example, four butanols titaniums, titanium tetraisopropylate, Dibutyltin oxide, dibutyl tin dilaurate, two stannous octoates, methyl ethyl diketone zirconium, or the mixture of these materials.
Catalyzer conventionally with 50 to 10000 ppm by weight, preferably the amount of 100 to 5000 ppm by weight adds, the alcohol of described amount based on used or the amount meter of alcohol mixture.
Can also be by adding suitable catalyzer and/or by selecting suitable temperature to control intermolecular polycondensation.In addition, the molecular-weight average of polymkeric substance (P) can regulate by composition and the residence time of starting ingredient.
Condensation product (K) and polycondensation product (P) are prepared at elevated temperatures, and it is conventionally at room temperature stable in a long time.
According to the character of condensation product (K), condensation reaction may produce the polycondensation product (P) with different structure, and it has side chain but be not crosslinked.In addition, polycondensation product (P) contains a carbonic ether focus group and ideally more than two OH groups or contain an OH focus group and more than two carbonate groups.The number of reactive group depends on character and the degree of polycondensation of used condensation product (K).For example, condensation product (K) thus also can react and form two kinds of different polycondensation products (P) by three intermolecular condensations.
In order to stop intermolecular polycondensation, there is multiple feasible method.For example temperature can be reduced to reaction stops and the temperature range of product (K) or polycondensation product (P) shelf-stable.
In another embodiment, once the intermolecular reaction of condensation product (K) generates the polycondensation product (P) with the required degree of polycondensation, by adding in product (P), have and can carry out termination reaction with the product of the group of the focus radical reaction of (P).For example, for carbonic ether focus group, for example, can add monoamine, diamines or polyamines.For hydroxyl focus group, can in product (P), add for example monoisocyanates, vulcabond or polyisocyanates, the compound that contains epoxide group, or can with the acid derivative of OH radical reaction.
High functionality polycarbonate of the present invention conventionally 0.1mbar to 20bar, preferably under the pressure of 1mbar to 5bar intermittently, prepare in the reactor of semi-batch or operate continuously or cascade reactor.
If the setting by above-mentioned reaction conditions and---suitable for---the selection of suitable solvent, product can carry out ensuing preparation process and purifying separately not after preparation.
In another preferred embodiment, described polycarbonate can not only contain the functional group having obtained by reaction, also contains other functional groups.In this case, functionalized can be in the process that molecular weight increases or thereafter, be to carry out after actual polycondensation finishes.
If before molecular weight increases or during add the component that also contains other functional groups or sense element except hydroxyl or carbonate group, obtain the carbonate polymer of the functional group except carbonate group and hydroxyl with stochastic distribution.
This effect can for example also contain other functional groups or sense element except hydroxyl or carbonate group compound by adding in polycondensation process is realized, and described other functional groups or sense element be sulfydryl, primary amino, secondary amino group or uncle's amino, ether, carboxylic acid derivative, sulfonic acid, phosphonate derivative, aryl or chain alkyl for example.In order to carry out modification with carbamate groups, can for example use product, 4-hydroxy piperidine, 1-hydroxyethyl piperazine, diethanolamine, dipropanolamine, diisopropanolamine (DIPA), three (methylol) aminomethane, three (hydroxyethyl) aminomethane, 1，2-diaminoethane, propylene diamine, hexamethylene-diamine or the isophorone diamine of the more high alkoxy degree of thanomin, Propanolamine, α-amino isopropyl alcohol, 2-(fourth is amino) ethanol, 2-(hexamethylene is amino) ethanol, 2-amino-n-butyl alcohol, 2-(2 '-amino ethoxy) ethanol or ammonia.
In order to use sulfydryl to carry out modification, can for example use mercaptoethanol.Tertiary amino can be by for example introducing N methyldiethanol amine, N-methyl dipropanolamine or N, N-dimethylethanolamine and generating.Ether can by for example in condensation course, introduce have two or more the Aethoxy Sklerol of high functionality generate.Can introduce chain alkyl with reacting of long alkanediol; Generate with reacting of two alkyl isocyanates or two aryl isocyanates the polycarbonate that contains alkyl, aryl and carbamate groups.
Ensuing functionalized can realization with suitable reacting of functionalized reagent by the high functionality hyperbranched polycarbonates of gained, described suitable functionalized reagent can react with OH and/or the carbonate group of polycarbonate.
The high functionality hyperbranched polycarbonates that contains hydroxyl can be for example by adding the molecule containing acidic group or isocyanate groups to be modified.Polycarbonate containing acidic group for example can be reacted and be obtained by the compound with containing anhydride group.
In addition, the high functionality polycarbonate of hydroxyl also can be by for example, reacting and be converted into high functionality polycarbonate-polyether glycol with oxirane---oxyethane, propylene oxide or butylene oxide ring---.
An important advance of the inventive method is its economy.Form the reaction of condensation product (K) or polycondensation product (P) and (K) or (P) can in a reaction unit, carry out with reacting of other functional groups or Element generation polycarbonate, this all has superiority technically and economically.
Hyper-branched polyester
As hyper-branched polyester, preferably use A 2b xthe hyper-branched polyester of type.A particularly preferably 2b 3the hyper-branched polyester of type.With AB 2the hyper-branched polyester of type is compared, these A 2b 3the polyester of type has the structure that rigidity is lower.So more preferred AB 2the hyper-branched polyester of type.
The hyper-branched polyester that is applicable to increase glossiness can pass through at least one aliphatics, annular aliphatic, aromatic-aliphatic or aromatic dicarboxylic acid (A 2) or derivatives thereof reacts acquisition with following substances:
A) at least one at least aliphatics, annular aliphatic, aromatic-aliphatic or aromatic alcohol (B of trifunctional 3), or
B) aliphatics of at least one divalence, annular aliphatic, aromatic-aliphatic or aromatic alcohol (B 2) and at least one contain aliphatics, annular aliphatic, aromatic-aliphatic or the aromatic alcohol (C more than the x valency of two OH groups x), x be greater than 2, preferably 3 to 8, more preferably 3 to 6, extremely preferred 3 to 4 number, more especially 3,
Or contain aliphatics, annular aliphatic, aromatic-aliphatic or the aromatic carboxylic acid (D more than two acidic groups by least one y) acquisition of reacting of or derivatives thereof and following compound, wherein y be greater than 2, preferably 3 to 8, more preferably 3 to 6, extremely preferred 3 to 4 number, more especially 3, described compound is:
C) aliphatics of at least one at least two sense, annular aliphatic, aromatic-aliphatic or aromatic alcohol (B 2), or
D) aliphatics of at least one divalence, annular aliphatic, aromatic-aliphatic or aromatic alcohol (B 2) and at least one contain aliphatics, annular aliphatic, aromatic-aliphatic or the aromatic alcohol (C more than the x valency of two OH groups x), x be greater than 2, preferably 3 to 8, more preferably 3 to 6, extremely preferred 3 to 4 number, more especially 3,
E) if be suitably under the existence of other functionalized unit E, and
F) optionally next react with monocarboxylic acid F,
The ratio of the reactive group in reaction mixture is chosen as and makes the mol ratio of OH group and carboxyl or derivatives thereof is 5:1 to 1:5, preferably 4:1 to 1:4, more preferably 3:1 to 1:3, extremely preferably 2:1 to 1:2.
Hyper-branched polyester mean in the present invention to contain hydroxyl and carboxyl and structurally with molecule on inhomogeneous non-crosslinked polyester all.The degree of crosslinking that non-crosslinked in this specification sheets means to exist is less than 15 % by weight, is preferably less than 10 % by weight, and its insoluble umber by polymkeric substance is determined.The insoluble umber of polymkeric substance is determined by the following method: use and gel permeation chromatography identical solvent used---be tetrahydrofuran (THF) or hexafluoroisopropanol, depend on which kind of solvent has better dissolving power to polymkeric substance---in Soxhlet equipment, carry out extracting for four hours, again residuum is dried to constant weight, and weighs the weight of residuum.
Dicarboxylic acid (A 2) comprise for example aliphatic dicarboxylic acid, for example oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane-α, alpha, omega-dicarboxylic acid, dodecane-α, alpha, omega-dicarboxylic acid, cis and trans cyclohexane-1,2-dicarboxylic acid, cis and trans cyclohexane-1,3-dicarboxylic acid, cis and trans cyclohexane-Isosorbide-5-Nitrae-dicarboxylic acid, cis and trans pentamethylene-1,2-dicarboxylic acid, cis and trans pentamethylene-1,3-dicarboxylic acid.Can also use in addition aromatic dicarboxylic acid, for example phthalic acid, m-phthalic acid and terephthalic acid.Can also use unsaturated dicarboxylic acid, for example toxilic acid or fumaric acid.
Described dicarboxylic acid also can be selected from following group and replace by one or more: C 1-C 10alkyl, C 3-C 12cycloalkyl, alkylidene group be methylene radical or ethylidene for example, or C 6-C 14aryl.The exemplary representative of the substituted dicarboxylic acid that can mention comprises following material: 2-Methylpropanedioic acid, 2-ethyl malonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethyl succsinic acid, 2-phenylsuccinic acid, methylene-succinic acid, 3,3-dimethylated pentanedioic acid.
Can also use the mixture of two or more above-mentioned dicarboxylic acid.
Described dicarboxylic acid can itself be used also and can its derivative form use.
C 1-C 4alkyl specifically means methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl, preferable methyl, ethyl and normal-butyl, more preferably methyl and ethyl, utmost point preferable methyl.
Can also use the mixture of dicarboxylic acid and one or more its derivatives.Can use the mixture of the two or more different derivatives of one or more dicarboxylic acid equally.
Particularly preferably use propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid or Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid (hexahydrobenzene dioctyl phthalate), phthalic acid, m-phthalic acid, terephthalic acid or its mono alkyl ester or dialkyl.
The tricarboxylic acid that can react or polycarboxylic acid (D y) example comprise equisetic acid, 1,3,5-hexanaphthene tricarboxylic acid, 1,2,4-benzene tricarbonic acid, 1,3,5-benzene tricarbonic acid, 1,2,4, the acid of 5-benzene tertacarbonic acid (1,2,4,5-pyromellitic acid) and mellitic acid and low-molecular-weight polypropylene.
Tricarboxylic acid or polycarboxylic acid (D y) can itself use also and can its derivative form use.
Derivative is corresponding acid anhydrides, mono alkyl ester or the dialkyl of monomer or polymer form, preferably single or two C 1-C 4alkyl ester, more preferably list or dimethyl ester or corresponding list or diethyl ester, and single and divinyl ester, also have mixed ester, preferably has different C 1-C 4the mixed ester of moieties, more preferably mixed methyl ethyl ester.
Can also use the mixture of tricarboxylic acid or polycarboxylic acid and one or more its derivatives, for example 1,2,4, the mixture of 5-pyromellitic acid and 1,2,4,5-pyromellitic acid dianhydride.Can use the mixture of the two or more different derivatives of one or more tricarboxylic acid or polycarboxylic acid equally, for example 1,3, the mixture of 5-hexanaphthene tricarboxylic acid and 1,2,4,5-pyromellitic acid dianhydride.
Glycol (the B using 2) comprise for example ethylene glycol, the third-1,2-glycol, the third-1,3-glycol, fourth-1,2-glycol, fourth-1,3-glycol, fourth-Isosorbide-5-Nitrae-glycol, fourth-2,3-glycol, penta-1,2-glycol, penta-1,3-glycol, penta-Isosorbide-5-Nitrae-glycol, penta-1,5-glycol, penta-2,3-glycol, penta-2,4-glycol, oneself-1,2-glycol, oneself-1,3-glycol, oneself-Isosorbide-5-Nitrae-glycol, oneself-1,5-glycol, oneself-1,6-glycol, oneself-2,5-glycol, heptan-1,2-glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,2-ethohexadiol, 1,9-nonanediol, 1,2-decanediol, decamethylene-glycol, 1,2-dodecanediol, 1,12-dodecanediol, 1,5-hexadiene-3,4-glycol, 1,2-ring pentanediol and 1,3-ring pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol and Isosorbide-5-Nitrae-cyclohexanediol, two (methylol) hexanaphthenes of 1,1-, two (methylol) hexanaphthenes of 1,2-, two (methylol) hexanaphthenes of 1,3-and Isosorbide-5-Nitrae-bis-(methylol) hexanaphthene, two (hydroxyethyl) hexanaphthenes of 1,1-, two (hydroxyethyl) hexanaphthenes of 1,2-, two (hydroxyethyl) hexanaphthenes of 1,3-and Isosorbide-5-Nitrae-bis-(hydroxyethyl) hexanaphthene, neopentyl glycol, (2)-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexylene glycol, 2,5-dimethyl-2,5-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, tetramethyl ethylene ketone, glycol ether, triglycol, dipropylene glycol, tripropylene glycol, polyoxyethylene glycol HO (CH 2cH 2o) n-H or polypropylene glycol HO (CH[CH 3] CH 2o) n---n is that integer and n>=4, polyethylene glycol-propylene glycol---order of oxyethane or propylene oxide units is blocked or random, polytetramethylene glycol---preferably have the molecular weight, poly--1 of the highest 5000g/mol to-H, ammediol---preferably there is molecular weight, the polycaprolactone of the highest 5000g/mol, or the mixture of the two or more representatives of above-claimed cpd.One or two hydroxyl in above-mentioned glycol can be substituted by SH group.The glycol preferably using is ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,2-cyclohexanediol, 1,3-cyclohexanediol and Isosorbide-5-Nitrae-cyclohexanediol, 1, two (methylol) hexanaphthenes and 1 of 3-, two (methylol) hexanaphthenes of 4-, and glycol ether, triglycol, dipropylene glycol and tripropylene glycol, polyoxyethylene glycol HO (CH 2cH 2o) n-H or polypropylene glycol HO (CH[CH 3] CH 2o) n---n is that integer and n>=4, polyethylene glycol-propylene glycol---order of oxyethane or propylene oxide units is blocked or random, or polytetramethylene glycol---preferably have the molecular weight of the highest 5000g/mol to-H.
Glycol B 2can optionally also comprise other functionality for example carbonyl, carboxyl, alkoxy carbonyl or alkylsulfonyl, for example dimethylol propionic acid or dimethylolpropionic acid, with and C 1-C 4alkyl ester, Zerol or glyceryl monooleate.
Alcohol (the C with at least three functionality x) comprise glycerine, Pehanorm, trimethylolethane, TriMethylolPropane(TMP), 1, 2, 4-trihydroxybutane, three (methylol) amine, triethanolamine, tripropanolamine, tetramethylolmethane, Glycerol dimer, the higher degree condenses of triglycerin or glycerine, two (TriMethylolPropane(TMP)s), two (tetramethylolmethanes), isocyanuric acid trishydroxymethyl ester, isocyanuric acid trihydroxyethyl ester (THEIC), isocyanuric acid three hydroxypropyl esters, inositol or sugar, glucose for example, fructose or sucrose, sugar alcohol is Sorbitol Powder for example, mannitol, threitol, tetrahydroxybutane, adonitol (ribitol), arabitol (lysol sugar alcohol), Xylitol, galactitol (melampyrum), maltose alcohol, Palatinitol (isomalt), functionality is three or higher, based on functionality, be three or higher alcohol and based on oxyethane, the Aethoxy Sklerol of propylene oxide and/or butylene oxide ring.
Particularly preferably glycerine, Glycerol dimer, triglycerin, trimethylolethane, TriMethylolPropane(TMP), two (TriMethylolPropane(TMP)), 1 herein, 2,4-trihydroxybutane, tetramethylolmethane, two (tetramethylolmethane), isocyanuric acid trihydroxyethyl ester, and the Aethoxy Sklerol based on oxyethane and/or propylene oxide.
Reaction can be carried out in the situation that not existing or having solvent.The example of suitable solvent comprises hydrocarbon for example paraffinic hydrocarbons, aromatics, ether and ketone.Preferably this reaction is carried out in the situation that not there is not solvent.Can under the existence of water-removal agent, carry out this reaction, described water-removal agent adds when reaction starts as additive.Suitable example comprises molecular sieve, especially molecular sieve mgSO 4and Na 2sO 4.Can also be by distilling and for example using water trap to remove water and/or alcohol in reaction process, in the situation that using water trap, water is removed by entrainment agent.
This reaction can be carried out in the situation that not there is not catalyzer.But preferably under the existence of at least one catalyzer, carry out.Described catalyzer is preferably acid organic catalyst, organo-metallic catalyst or organic catalyst, or the mixture of two or more acid organic catalyst, organo-metallic catalyst or organic catalyst.
For acid organic catalyst of the present invention, be for example sulfuric acid, vitriol and hydrosulfate for example sodium pyrosulfate, phosphoric acid, phosphonic acids, Hypophosporous Acid, 50, hydrazine aluminum sulfate, alum, acidic silica gel (pH≤6, especially≤5) and acidic alumina.Other spendable acid organic catalysts comprise that for example general formula is Al (OR 1) 3aluminum compound, and titanate.Preferred acid organo-metallic catalyst is for example the ester of dialkyltin or dialkyl tin.Preferred acid organic catalyst is to contain for example acidic organic compound of bound phosphate groups, sulfonic acid group, sulfate group or phosphonyl group.Also can be by acid ion exchangers as acid organic catalyst.
This reaction is carried out at the temperature of 60 to 250 ℃.
The hyper-branched polyester that the present invention uses has at least 500, preferably at least 600, the more preferably molecular weight M of 1000g/mol w.Molecular weight M wthe upper limit be preferably 500000g/mol; Particularly preferably be no more than 200000, the utmost point is particularly preferably no more than 100000g/mol.
Polydispersity and number-average molecular weight and weight-average molecular weight M nand M wnumerical value by gel permeation chromatography, use polymethylmethacrylate as standard substance and use tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE or hexafluoroisopropanol to measure as eluent here.The method is described in Analytiker Taschenbuch, vol.4, and pages 433 to 442, Berlin 1984.
The polydispersity of the polyester that the present invention uses is generally 1.2 to 50, and preferably 1.4 to 40, more preferably 1.5 to 30, extremely preferably 2 to 30.
Hyperbranched poly carbamate
The scope of term used herein " polyurethane(s) " has exceeded the implication of conventional understanding, comprises can obtaining with active hydrogen compounds reaction by vulcabond or polyisocyanates and can be by carboxylamine ester structure and polymkeric substance that for example urea, allophanate, biuret, carbodiimide, acid amides, uretonimine (uretonimine), urea diketone (uretdione), isocyanuric acid ester or oxazolidone structure are connected.
The hyperbranched poly carbamate that the present invention uses can be used and contains isocyanate groups and can react to form with isocyanate groups the AB of the group being connected xmonomer is synthetic.Hyperbranched poly carbamate for synthetic the present invention uses, can also be used monomer binding substances, and this monomer binding substances is first as the formation AB of intermediate xstructural sections, wherein x is 2 to 8 natural number, preferably 2 or 3.This hyperbranched poly carbamate and be described in WO97/02304 for the preparation of its method is included in herein by reference.Suitable hyperbranched poly carbamate also can by vulcabond and/or polyisocyanates with there are at least two and can obtain with the reacting of compound of the group of isocyanate reaction, wherein at least one reactant contains reactive different from the functional group of another reactant functional groups, and reaction conditions is chosen as and makes to only have some reactive group to react each other in each reactions steps.Such hyperbranched poly carbamate and be described in EP 1026185 for the preparation of its method is included in herein by reference.
Describedly can be preferably with the group of isocyanate reaction OH-, NH 2-, NHR-or SH group.
AB xmonomer can be prepared by conventional methods.AB xmonomer can for example be used blocking group technology to synthesize by the method described in WO 97/02304.This technology can be by preparing AB by 2,4 toluene diisocyanate (TDI) and TriMethylolPropane(TMP) 2the process of monomer is carried out example explanation.First, TDI isocyanate groups for example reacts and is closed with oxime in a usual manner.Remaining free NCO group reacts with TriMethylolPropane(TMP), but only have one in three OH groups, reacts with isocyanate groups, and all the other two OH groups are closed by acetalization.Remove blocking group and obtain the molecule with an isocyanate groups and two OH groups.
A particularly advantageous synthetic AB xthe mode of molecule is to use the method described in DE-A 19904444, and group does not wherein need protection.In the method, use vulcabond or polyisocyanates, its with there are at least two and can react with the compound of the group of isocyanate reaction.At least one reactant contains reactive different from another reactant groups.Preferably, two kinds of reactants all contain reactive different from another reactant groups.Reaction conditions is chosen as and makes to only have some reactive group to react each other.
Available vulcabond and polyisocyanates comprise aliphatics well known in the prior art, annular aliphatic and aromatic isocyanate.Preferred vulcabond and polyisocyanates are 4, mixture, the tetramethylene diisocyanate, 1 of the diphenylmethanediisocyanate of the diphenylmethanediisocyanate of 4 '-diphenylmethanediisocyanate, monomeric form and oligopolymer form (polymkeric substance MDI), hexamethylene-diisocyanate, 4,4 '-methylene-bis (cyclohexyl) vulcabond, xylylene diisocyanate, tetramethyl xylylene diisocyanate, dodecyl vulcabond, Methionin alkylene diisocyanate---wherein alkyl is C 1-C 10alkyl, 2,2,4-trimethylammonium-1,6-hexamethylene diisocyanate or 2,4,4-trimethylammonium-1,6-hexamethylene diisocyanate, Isosorbide-5-Nitrae-cyclohexyl diisocyanate or 4-isocyanatomethyl-1,8-eight methylene diisocyanates.
Vulcabond or the polyisocyanates particularly preferably with reactive different NCO groups, for example 2, 4-tolylene diisocyanate (2, 4-TDI), 2, 4 '-'-diphenylmethane diisocyanate (2, 4 '-MDI), toluene triisocyanate, isophorone diisocyanate (IPDI), 2-butyl-2-ethyl pentamethylene diisocyanate, 2-propyl isocyanate base cyclohexyl isocyanate, 3 (4)-isocyanatomethyls-1-isocyanatomethyl, 1, close-4-of 4-bis-isocyanic acids methylpentane, 2, 4 '-methylene-bis (cyclohexyl) vulcabond and 4-methylcyclohexane 1, 3-vulcabond (H-TDI).Such isocyanic ester (b) particularly preferably also, its NCO group has identical reactivity when initial but addition alcohol or amine can cause reactive reduction of the 2nd NCO group for the first time to NCO group.The example is that NCO group is by the isocyanic ester of delocalized electron system coupling, for example 1,3-phenylene diisocyanate and Isosorbide-5-Nitrae-phenylene diisocyanate, 1,5-naphthalene diisocyanate, diphenyl diisocyanate, tolidine vulcabond or 2,6-tolylene diisocyanate.
For example can also use low polymeric polyisocyanate or the polymeric polyisocyanate that can be prepared by described vulcabond or polyisocyanates or its mixture, described low polymeric polyisocyanate or polymeric polyisocyanate are connected by carbamate, allophanate, urea, biuret, urea diketone, acid amides, isocyanuric acid ester, carbodiimide, uretonimine, oxadiazine triketone or iminooxadiazinedionepolyisocyanates diketone structure.
Used have at least two and can be preferably its functional group to two different senses of the reactivity of NCO group, trifunctional or four functional compounds from the compound of the group of isocyanate reaction.The compound preferably with at least one primary hydroxyl and at least one secondary hydroxyl, at least one hydroxyl and at least one sulfydryl, particularly preferably in molecule, there is at least one hydroxyl and at least one amino compound, especially amino alcohol, aminodiol and amino triol, because amino more obvious more easily and isocyanate reaction than hydroxyl.
It is described that to have at least two can be propylene glycol, glycerol, mercaptoethanol, thanomin, N-Mono Methyl Ethanol Amine, diethanolamine, ethanol propanol amine, dipropanolamine, diisopropanolamine (DIPA), 2-amino-1 with the example of the compound of the group of isocyanate reaction, ammediol, AMPD or three (methylol) aminomethane.Also can use the mixture of described compound.
AB 2the preparation of molecule can be carried out example explanation with reacting of aminodiol by vulcabond.First one mole of vulcabond reacts at low temperatures with one mole of aminodiol, preferably in the scope of-10 to 30 ℃.The reaction that forms carbamate is substantially completely suppressed in this temperature range, and the higher NCO group of reactivity in isocyanic ester only reacts with the amino in aminodiol.The AB forming xmolecule has a free NCO group and two free OH groups, can be for the synthesis of highly branched polyurethane(s).
When heating and/or adding catalyzer, this AB 2molecule can carry out intermolecular reaction, the polyurethane(s) of height of formation branching.The synthetic of hyperbranched poly carbamate can advantageously do not isolated AB in advance xin the situation of molecule, further carrying out at elevated temperatures in reactions steps, the temperature of described rising is preferably in the scope of 30 to 80 ℃.Use the above-mentioned AB with two OH groups and a NCO group 2molecule can generate the hyperbranched polymer that per molecule has the OH group of a free NCO group and---depending on the polymerization degree---some amount.This reaction can be carried out paramount degree of conversion to generate the structure of ultra high molecular weight.But also can for example by adding suitable monofunctional compound or passing through, add for the preparation of AB 2one of initial compounds of molecule interrupts reaction when having reached desired molecule amount.According to the initial compounds for termination reaction, can obtain the molecule of complete NCO end-blocking or the molecule of complete OH end-blocking.
Or, also can be for example by one mole of glycerol and 2 mole 2,4-TDI prepares AB 2molecule.Primary alcohol group and 4 s' the preferential reaction at low temperatures of isocyanate groups forms the adducts with an OH group and two isocyanate groups, this adducts as described under higher temperature, be converted into hyperbranched poly carbamate.Its initial hyperbranched polymer that generates the NCO group with a free OH group and---depending on the polymerization degree---some amount.
Hyperbranched poly carbamate can be prepared conventionally in solvent-free situation, but preferably in solution, prepares.It is at room temperature compound liquid and that be inertia to described monomer and polymkeric substance that available solvent generally includes all.
Can obtain other products by further synthetic schemes.Can be for example by vulcabond with there are at least 4 and can react and obtain AB with the compound of the group of isocyanate reaction 3molecule.An example is reacting of 2,4 toluene diisocyanate and three (methylol) aminomethane.
Polyreaction also can be with stopping with the polyfunctional compound of A radical reaction separately.Thereby a plurality of little super branched molecules can be coupled together to form large super branched molecule.
The hyperbranched poly carbamate with the branch that chain is extended can for example obtain as follows, except using AB xbeyond molecule, the vulcabond that is also 1:1 by mol ratio and there are two and can obtain in polyreaction with the compound of the group of isocyanate reaction.The AA that these are extra or BB compound also can have other functional group, but these functional groups must can not be under selected reaction conditions and A or B radical reaction.This makes it possible to introduce other functional groups in hyperbranched polymer.
Other synthetic schemess for hyperbranched poly carbamate are disclosed in DE 10013187 and DE 10030869.
The functional group of the hyperbranched poly carbamate obtaining by building-up reactions as mentioned above, also can be hydrophobic, hydrophilization or functional group's displacement (transfunctionalization).According to its reactivity, the hyperbranched poly carbamate that contains isocyanate groups is particularly useful for functional group's displacement.Can also be by suitable reaction compatibility material to OH end-blocking or NH 2the polyurethane(s) of end-blocking carries out functional group's displacement.
The group of preferably introducing hyperbranched poly carbamate is-COOH ,-CONH 2,-OH ,-NH 2,-NHR ,-NR 2,-NR 3 +,-SO 3h and salt thereof.
The group with the H atom of enough acidity can be converted into by the alkaline purification with suitable corresponding salt.Similarly, base groups can be used suitable acid to be converted into corresponding salt.Therefore can obtain water-soluble hyperbranched poly carbamate.
By making the product of NCO end-blocking and alkohol and amine, especially thering is C 8-C 40the alkohol and amine reaction of alkyl, can obtain hydrophobization product.
Hydrophilic but non-ionic product can pass through the polymkeric substance of NCO end-blocking react acquisition with Aethoxy Sklerol, described Aethoxy Sklerol is glycol ether, triglycol, Tetraglycol 99 or polyoxyethylene glycol for example.
Acidic group can be for example by reacting and be included into hydroxycarboxylic acid, hydroxyl sulfoacid or amino acid.The example of suitable reaction compatibility thing is 2-oxyacetic acid, 4-HBA, sabinic acid, 2-ethylenehydrinsulfonic acid, glycine or L-Ala.
Can also generate the hyperbranched poly carbamate with different functionality.This can be by for example with the mixture reaction of multiple compounds or by only making the initial functional group existing of a part, for example only a part of OH and/or NCO radical reaction are realized.
Functional group's displacement of hyperbranched poly carbamate can advantageously be carried out immediately and in advance the polyurethane(s) of NCO end-blocking do not separated after polyreaction.But functionalizedly also can in other reaction, carry out.
The hyperbranched poly carbamate using in the present invention on average has at least 4 and be no more than 100Ge functional group conventionally.Described hyperbranched poly carbamate preferably has 8 to 80, more preferably 8 Zhi50Ge functional groups.The weight-average molecular weight M of the hyperbranched poly carbamate preferably using wbe 1000 to 500000g/mol, preferably 5000 to 200000g/mol, and more preferably 10000 to 100000g/mol.
Hyperbranched polyureas
Can as the hyperbranched polyureas of high functionality that increases the component of glossiness, can be reacted and be obtained by the amine that for example makes one or more carbonic ethers and one or more have at least two primary aminos and/or secondary amino group in the present invention, wherein at least one amine has at least three primary aminos and/or secondary amino group.
Suitable carbonic ether is aliphatics, aromatic series or mixing-in fat family-aromatic carbonate; Preferred aliphat carbonic ether, for example, have C 1-C 12the dialkyl carbonate of alkyl.Example is ethylene carbonate, 1, the two dodecyl esters of 2-Texacar PC or 1,3-Texacar PC, diphenyl carbonate, carboxylol ester, carbonic acid dinaphthyl ester, carbonic acid ethyl phenyl ester, dimethyl benzyl, methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, carbonic acid diisobutyl ester, diamyl carbonate, carbonic acid dihexyl, carbonic acid two heptyl esters, carbonic acid dioctyl ester, carbonic acid didecyl ester or carbonic acid.The carbonic ether particularly preferably using is methylcarbonate, diethyl carbonate, dibutyl carbonate and carbonic acid diisobutyl ester.
Carbonic ether reacts with the amine that one or more have at least two primary aminos and/or secondary amino group, and wherein at least one amine has at least three primary aminos and/or secondary amino group.The amine with two primary aminos and/or secondary amino group produces chainpropagation in polyureas, and the amine with three or more primary aminos or secondary amino group causes the branching of the hyperbranched polyureas of gained high functionality.
The suitable amine with two primary aminos or secondary amino group that can react with carbonate group or carbamate groups is for example quadrol, N-alkyl quadrol, propylene diamine, 2, 2-dimethyl-1, 3-propylene diamine, N-alkyl propylene diamine, butanediamine, N-alkyl butanediamine, pentamethylene diamine, hexanediamine, N-alkyl hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, dodecane diamines, n-Hexadecane diamines, tolylene diamine, dimethylphenylene diamine, diaminodiphenyl-methane, diamino-dicyclohexyl methane, phenylenediamine, cyclohexanediamine, two (amino methyl) hexanaphthene, diamino diphenyl sulfone, isophorone diamine, 2-butyl-2-ethyl-1, 5-five methylene diamine, 2, 2, 4-trimethylammonium-1, 6-hexanediamine or 2, 4, 4-trimethylammonium-1, 6-hexanediamine, 2-aminopropyl cyclo-hexylamine, 3 (4)-aminomethyl-1,2s-methylcyclohexyl amine, 1, 4-diamino-4-methylpentane, the polyoxyalkylene polylol (being called Jeffamine) of amine end-blocking or the polytetramethylene glycol of amine end-blocking.
Described amine preferably has two primary aminos, quadrol for example, propylene diamine, 2, 2-dimethyl-1, 3-propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, dodecane diamines, n-Hexadecane diamines, tolylene diamine, dimethylphenylene diamine, diaminodiphenyl-methane, diamino-dicyclohexyl methane, phenylenediamine, cyclohexanediamine, diamino diphenyl sulfone, isophorone diamine, two (amino methyl) hexanaphthene, 2-butyl-2-ethyl-1, 5-pentamethylene diamine, 2, 2, 4-trimethylammonium-1, 6-hexanediamine or 2, 4, 4-trimethylammonium-1, 6-hexanediamine, 2-aminopropyl cyclo-hexylamine, 3 (4)-aminomethyl-1,2s-methylcyclohexyl amine, 1, 4-diamino-4-methylpentane, the polyoxyalkylene polylol (being called Jeffamine) of amine end-blocking or the polytetramethylene glycol of amine end-blocking.
Particularly preferably butanediamine, pentamethylene diamine, hexanediamine, tolylene diamine, dimethylphenylene diamine, diaminodiphenyl-methane, diamino-dicyclohexyl methane, phenylenediamine, cyclohexanediamine, diamino diphenyl sulfone, isophorone diamine, two (amino methyl) hexanaphthene, the polyoxyalkylene polylol (being called Jeffamine) of amine end-blocking or the polytetramethylene glycol of amine end-blocking.
The suitable amine with three above primary aminos and/or secondary amino group that can react with carbonate group or carbamate groups is for example three (amino-ethyl) amine, three (aminopropyl) amine, three (amino hexyl) amine, triamino hexane, 4-aminomethyl-1,2, 8-octamethylenediamine, triaminononane, two (amino-ethyl) amine, two (aminopropyl) amine, two (aminobutyl) amine, two (amino amyl group) amine, two (amino hexyl) amine, N-(2-amino-ethyl) propylene diamine, trimeric cyanamide, oligomeric diaminodiphenyl-methane, N, N '-bis-(3-aminopropyl) quadrol, N, N '-bis-(3-aminopropyl) butanediamine, N, N, N ', N '-tetra-(3-aminopropyl) quadrol, N, N, N ', N '-tetra-(3-aminopropyl) butanediamine, functionality is three or the polyoxyalkylene polylol (being called Jeffamine) of higher amine end-blocking, functionality be three or higher polymine or functionality be three or higher polypropylen(e)imine.
The amine preferably with three above primary aminos and/or secondary amino group is three (amino-ethyl) amine, three (aminopropyl) amine, three (amino hexyl) amine, triamino hexane, 4-aminomethyl-1,2, and 8-octamethylenediamine, triaminononane, two (amino-ethyl) amine, two (aminopropyl) amine, two (aminobutyl) amine, two (amino amyl group) amine, two (amino hexyl) amine, N-(2-amino-ethyl) propylene diamine, trimeric cyanamide or functionality are three or the polyoxyalkylene polylol (being called Jeffamine) of higher amine end-blocking.
The amine particularly preferably with three or more primary aminos, for example three (amino-ethyl) amine, three (aminopropyl) amine, three (amino hexyl) amine, triamino hexane, 4-aminomethyl-1,2,8-octamethylenediamine, triaminononane or functionality are three or the polyoxyalkylene polylol (being called Jeffamine) of higher amine end-blocking.
To know, the mixture of described amine also can be used.
Conventionally not only use the amine with two primary aminos or secondary amino group, also use the amine with three or more primary aminos or secondary amino group.This amine mixt also can characterize by its average amine functionality, and non-reacted tertiary amino is not counted in.Therefore, such as diamines and triamine etc. the average functionality of molar mixture be 2.5.Preferably average amine functionality is the present invention's reaction of 2.1 to 10, particularly 2.1 to 5 amine mixt.
Alcohol or phenol that the reaction of the hyperbranched polyureas of high functionality that carbonic ether is used with diamines or polyamines formation the present invention is connected by cancellation carbonic ether complete.If a part carbonic ether and two are amino, react, cancellation two molecule alcohol or phenol generate a urea groups.If a part carbonic ether only reacts with an amino, generate carbamate groups cancellation a part alcohol or phenol.
A kind of carbonic ether or multiple carbonic ether can carry out with reacting of a kind of amine or various kinds of amine in solvent.In this case, conventionally can use any solvent that is inertia to each reactant.Preferably in organic solvent, carry out, described organic solvent is decane, dodecane, benzene, toluene, chlorobenzene, dichlorobenzene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE or solvent naphtha for example.
In a preferred embodiment, reaction is carried out in body, there is no inert solvent.If the alcohol discharging in the reaction between amine and carbonic ether or carbamate or phenol can be isolated, thereby be removed from molecular balance by distillation---being suitably under the pressure of reduction---.This also can add fast response.
In order to accelerate the reaction between amine and carbonic ether or carbamate, also can add catalyzer or catalyst mixture.Suitable catalyzer is generally the compound of the formation of catalytic amino manthanoate or urea, for example alkali metal hydroxide or alkaline earth metal hydroxides, alkali metal hydrocarbonate or alkali metal bicarbonates, alkaline carbonate or alkaline earth metal carbonate, tertiary amine, ammonium compound, or the organic compound of aluminium, tin, zinc, titanium, zirconium or bismuth.For example can use the oxyhydroxide of lithium, sodium, potassium or caesium, Quilonum Retard, sodium carbonate, salt of wormwood or cesium carbonate, diazabicyclo octane (DABCO), diazabicyclo-nonene (DBN), diazabicyclo undecylene (DBU), imidazoles is imidazoles, 1-Methylimidazole, glyoxal ethyline and 1,2 dimethylimidazole for example, four butanols titaniums, Dibutyltin oxide, dibutyl tin dilaurate, two stannous octoates, methyl ethyl diketone zirconium, or the mixture of these materials.
Catalyzer conventionally with 50 to 10000 ppm by weight, preferably the amount of 100 to 5000 ppm by weight adds, the amount meter of the amine of described amount based on used.
After reaction (not carrying out further modification), the high functionality of preparing with present method is amino or carbamate groups end-blocking for hyperbranched polyureas.It can easily be dissolved in polar solvent, water for example, and alcohol is methyl alcohol, ethanol, butanols for example, alcohol/water mixture, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, ethylene carbonate or Texacar PC.
For the hyperbranched polyureas of high functionality of the present invention, be to contain urea groups and at least four, preferred at least six, the product of Ba Ge functional group at least particularly.Conventionally the number of functional group does not have the upper limit, but the product with very many functional groups may demonstrate undesired character, for example high viscosity or low solubility.The high functionality polyureas that the present invention uses has the 100Ge of being no more than functional group conventionally, is preferably no more than 30Ge functional group.The implication of functional group is primary amino, secondary amino group or tertiary amino or carbamate groups herein.In addition, the hyperbranched polyureas of high functionality can contain other functional groups, and described other functional groups do not participate in synthetic (the seeing below) of hyperbranched polymer.These other functional groups can introduce by also contain diamines or the polyamines of other functional groups except primary amino and secondary amino group.
The polyureas that the present invention uses can contain other functional groups.In the functionalized process that can react with a kind of amine or various kinds of amine at carbonic ether in this case, carry out, in the polycondensation process increasing at molecular weight, carry out, or after polycondensation finishes, follow-up functionalized by gained polyureas is carried out.
If before molecular weight increases or during add the component that also contains other functional groups except amino or carbamate groups, product is to contain other of stochastic distribution---except carbamate groups or amino---polyureas of functional group.
For example, before polycondensation or during, can add the component that also contains hydroxyl, sulfydryl, uncle's amino, ether, carboxyl, sulfonic group, phosphonate group, aryl or chain alkyl except amino or carbamate groups.
The component that can be added for functionalized hydroxyl comprises for example product, 4-hydroxy piperidine, 1-hydroxyethyl piperazine, diethanolamine, dipropanolamine, diisopropanolamine (DIPA), three (methylol) aminomethane or three (hydroxyethyl) aminomethane of the more high alkoxy degree of thanomin, N-Mono Methyl Ethanol Amine, Propanolamine, α-amino isopropyl alcohol, butanolamine, 2-amino-n-butyl alcohol, 2-(fourth is amino) ethanol, 2-(hexamethylene is amino) ethanol, 2-(2 '-amino ethoxy) ethanol or ammonia.
Can be added for the functionalized component containing sulfydryl and comprise for example cysteamine.Can be by using for example N-methyl diethylenetriamine or N, N-dimethyl-ethylenediamine carries out tertiary aminofunctional by hyperbranched polyureas.It is functionalized that Aethoxy Sklerol (being called Jeffamine) that can be by using amine end-blocking carries out ether by hyperbranched polyureas.Can be functionalized by for example using aminocarboxylic acid, thionamic acid or aminophosphonic acid that hyperbranched polyureas is carried out to acidic group.Can having the alkylamine of chain alkyl or alkyl isocyanate by use, that hyperbranched polyureas is carried out to chain alkyl is functionalized.
Polyureas also can be undertaken functionalized by the monomer that uses a small amount of containing to be different from the functional group of amino or carbamate groups.Now can mention and for example have two, three or the alcohol of high functionality more, described alcohol can be included into polyureas by carbonic ether or carbamate-functional.Therefore, for example can be by adding alkane glycol, enediol or the alkyne diol of long-chain to obtain hydrophobicity, and polyethylene oxide glycol or triol make polyureas have wetting ability.
Described before polycondensation or during the functional group except amine, carbonic ether or carbamate groups that introduces conventionally with 0.1 to 80mol%, preferably 1 to 50mol% amount, introduce, the total amount meter of described amount based on amino, carbamate and carbonate group.
Containing the amino hyperbranched polyureas of high functionality follow-up functionalized can by for example add containing the molecule of acidic group, isocyanate groups, ketone group or aldehyde radical or containing the two keys of activation for example the molecule of acrylic double bond realize.For example,, and if can be by being then hydrolyzed to obtain the polyureas containing acidic group with reacting of vinylformic acid or toxilic acid and derivative thereof is suitable.
In addition, can by containing the amino hyperbranched polyureas of high functionality by for example oxyethane, propylene oxide or butylene oxide ring react and be converted into high functionality polyurea polylol with oxirane.
Form salt with protonic acid or for example methyl halide or sulfuric acid dialkyl carry out the quaternized hyperbranched polyureas of high functionality that makes to amido functional group and dissolve in or dispersible in water with alkylating reagent.
In order to carry out hydrophobization, can make the hyperbranched polyureas of high functionality and saturated or unsaturated long-chain carboxylic acid, its derivative that can react with amine groups or aliphatics or aromatic isocyanate reaction of amine end-blocking.
The polyureas of carbamate groups end-blocking can be by reacting and hydrophobization with chain alkyl An Huo long-chain fat family monohydroxy-alcohol.
Ultrabranching polyamide
Suitable ultrabranching polyamide can be by making to have the first monomer A of at least two functional group A 2with there is at least the second monomers B of the B of San Ge functional group 3reaction preparation, wherein
1) functional group A and B react each other, and
2) one of monomer A and B are that amine and another are carboxylic acid or acrylate.
Suitable ultrabranching polyamide comprises over-branched polyamidoamine (referring to EP-A 802215, US 2003/0069370A1 and US 2002/0161113A1).
Although the first monomer A 2also can have more than two functional group A, but herein for writing for purpose of brevity A 2although, and the second monomers B 3also can there is the B more than San Ge functional group, but herein for writing for purpose of brevity B 3.Important factor is only A 2and B 3functionality different.
According to condition 1), functional group A and B react each other.So the selection of functional group A and B should make A not react (or only with inapparent degree reaction) with A and B does not react (or only with inapparent degree reaction) with B, but A reacts with B.
According to condition 2), one of monomer A and B are that amine and another are carboxylic acid.
Preferably, monomer A 2for thering is the carboxylic acid of at least two carboxyls, and monomers B 3for thering are at least three amino amine.Or monomer A 2for thering are at least two amino amine, and monomers B 3for thering is the carboxylic acid of at least three carboxyls.
Suitable carboxylic acid has 2 to 4 conventionally, 2 or 3 carboxyls particularly, and has alkyl, aryl or the arylalkyl containing 1 to 30 C atom.
The example of spendable dicarboxylic acid is: oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane-α, alpha, omega-dicarboxylic acid, dodecane-α, alpha, omega-dicarboxylic acid, cis and trans cyclohexane-1,2-dicarboxylic acid, cis and trans cyclohexane-1,3-dicarboxylic acid, cis and trans cyclohexane-1,4-dicarboxylic acid, cis and trans pentamethylene-1,2-dicarboxylic acid and cis and trans pentamethylene-1,3-dicarboxylic acid, described dicarboxylic acid also can be selected from following group and replace by one or more: C 1-C 10alkyl, C 3-C 12cycloalkyl, alkylidene group and C 6-C 14aryl.The example of the substituted dicarboxylic acid that can mention is: 2-Methylpropanedioic acid, 2-ethyl malonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethyl succsinic acid, 2-phenylsuccinic acid, methylene-succinic acid and 3,3-dimethylated pentanedioic acid.
Other suitable compounds are ethylenic unsaturated dicarboxylic acid, for example toxilic acid and fumaric acid, and aromatic dicarboxylic acid, for example phthalic acid, m-phthalic acid or terephthalic acid.
Suitable tricarboxylic acid or the example of tetracarboxylic acid are 1,3,5-benzenetricarboxylic acid, TMLA, 1,2,4,5-pyromellitic acid, butane tricarboxylic acid, naphthalene tricarboxylic acid and hexanaphthene-1,3,5-tricarboxylic acid.
Can also use the mixture of two or more above-mentioned carboxylic acids.Described carboxylic acid can itself be used also and can its derivative form use.Described derivative particularly
The acid anhydrides of-described carboxylic acid, especially monomeric form or polymer form;
The ester of-described carboxylic acid, for example
● mono alkyl ester or dialkyl, preferably mono-methyl or dimethyl ester, or corresponding mono ethyl ester or diethyl ester, or by mono alkyl ester or dialkyl that more higher alcohols generates, described more higher alcohols is n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, n-hexyl alcohol for example
● single vinyl acetate and divinyl ester, and
● mixed ester, preferable methyl ethyl ester.
Can also use the mixture of two or more different derivatives of the mixture that formed by carboxylic acid and one or more its derivatives or one or more dicarboxylic acid.
Carboxylic acid used more preferably comprises succsinic acid, pentanedioic acid, hexanodioic acid, cyclohexane dicarboxylic acid, phthalic acid, m-phthalic acid, terephthalic acid, or its mono-methyl or dimethyl ester.The utmost point is succsinic acid and hexanodioic acid particularly preferably.
Suitable amine has 2 to 6 conventionally, 2 to 4 amino particularly, and alkyl, aryl or the arylalkyl with 1 to 30 C atom.
The example of available diamines is formula R 1-NH-R 2-NH-R 3diamines, R wherein 1, R 2and R 3be hydrogen or alkyl, aryl or the arylalkyl with 1 to 20 C atom independently of one another.Described alkyl can be straight chain or particularly for R 2also can be ring-type.
The example of suitable diamines is quadrol, propylene diamine (1, 2-diaminopropanes and 1, 3-diaminopropanes), N-methyl ethylenediamine, piperazine, tetramethylene-diamine (1, 4-diaminobutane), N, N '-dimethyl-ethylenediamine, NEED, 1, 5-1,5-DAP, 1, 3-diamino-2, 2-diethyl propane, 1, two (methylamino-) propane of 3-, hexamethylene-diamine (1, 6-diamino hexane), 1, 5-diamino-2-methylpentane, 3-(the third amino) propylamine, N, N '-bis-(3-aminopropyl) piperazine, N, N '-bis-(3-aminopropyl) piperazine, and isophorone diamine (IPDA).
Suitable triamine, tetramine or the more example of the amine of high functionality are three (2-amino-ethyl) amine, three (2-aminopropyl) amine, diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), isopropylidene triamine, dipropylenetriamine and N, N '-bis-(3-aminopropyl quadrol).
Aminobenzyl amine and the amino hydrazides with 2 or more amino are also suitable.
Amine used particularly preferably comprises DETA or three (2-aminopropyl) amine or its mixture.
Can also use the mixture of two or more carboxylic acids or carboxylic acid derivative or the mixture of two or more amine.The functionality of described various carboxylic acid or amine can be identical or different.
Particularly, if monomer A 2for diamines, monomers B used 3the mixture that can comprise dicarboxylic acid and tricarboxylic acid (or more the carboxylic acid of high functionality), mixture B 3average functionality be at least 2.1.The average functionality of the mixture for example, being comprised of 50mol% dicarboxylic acid and 50mol% tricarboxylic acid is 2.5.
Similarly, if monomer A 2for dicarboxylic acid, monomers B used 3the mixture that can comprise diamines and triamine (or more the amine of high functionality), mixture B 3average functionality be at least 2.1.This scheme is particularly preferred.The average functionality of the mixture for example, being comprised of 50mol% diamines and 50mol% triamine is 2.5.
Monomer A 2the reactivity of functional group A can be identical also can be different.Equally, monomers B 3the reactivity of the B of functional group can be identical also can be different.Particularly, monomer A 2two amino reactivities or monomers B 3three amino reactivities can be identical or different.
In a preferred embodiment, carboxylic acid is two functional monomer A 2, amine is trifunctional monomer B 3, this means preferred use dicarboxylic acid and triamine or the amine of high functionality more.
Monomer A used 2more preferably comprise dicarboxylic acid, monomers B used 3more preferably comprise triamine.Monomer A used 2the utmost point preferably includes hexanodioic acid and monomers B used 3the utmost point preferably includes diethylenetriamine or three (2-amino-ethyl) amine.
In monomer A 2and B 3polymerization to be to generate in the process of ultrabranching polyamide or afterwards, also can use two senses or more the monomer C of high functionality as chain extension agent.This jellying point that makes to control polymkeric substance (forms the cross-linking set of insoluble gel particle by crosslinking reaction; For example, referring to Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, pp.387-398), and change macromolecular structure, i.e. the connection of monomer side chain.
Therefore, present method preferred embodiment is also in monomer A 2and B 3between the reaction period or be used as afterwards the monomer C of chain extension agent.
The example of suitable chain monomer C is above-mentioned diamines or the amine of high functionality more, thereby it connects from the carboxyl reaction of different polymkeric substance side chains.Specially suitable compound is isophorone diamine, quadrol, 1, 2-diaminopropanes, 1, 3-diaminopropanes, N-methyl ethylenediamine, piperazine, tetramethylene-diamine (1, 4-diaminobutane), N, N '-dimethyl-ethylenediamine, NEED, 1, 5-1,5-DAP, 1, 3-diamino-2, 2-diethyl propane, 1, two (methylamino-) propane of 3-, hexamethylene-diamine (1, 6-diamino hexane), 1, 5-diamino-2-methylpentane, 3-(the third amino) propylamine, N, N '-bis-(3-aminopropyl) piperazine, N, N '-bis-(3-aminopropyl) piperazine and isophorone diamine (IPDA).
General formula H 2the amino acid of N-R-COOH is also suitable as chain extension agent C, and wherein R is organic group.
The amount of chain extension agent C depends on required jellying point or required macromolecular structure conventionally.The amount of chain extension agent C is generally 0.1 % by weight to 50 % by weight, and preferably 0.5 % by weight to 40 % by weight, particularly 1 % by weight to 30 % by weight, based on monomer A used 2and B 3total amount meter.
In order to prepare functionalized poly acid amides, also use simple function comonomer D, it can be in monomer A 2and B 3reaction before, during or add afterwards.The method obtains by the polymkeric substance of copolymerization units and functional group's chemistry modification thereof.
Therefore a preferred embodiment of present method is in monomer A 2and B 3reaction before, during or use afterwards and there is the comonomer D of functional group, and generate modified polyamide.
The example of described comonomer D is saturated or unsaturated monocarboxylic, comprises lipid acid, and acid anhydrides or ester.Suitable sour example is acetic acid, propionic acid, butyric acid, valeric acid, isopropylformic acid, trimethylacetic acid, caproic acid, sad, enanthic acid, capric acid, n-nonanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, montanic acid, stearic acid, Unimac 5680, n-nonanoic acid, 2 ethyl hexanoic acid, phenylformic acid, and unsaturated monocarboxylic, methacrylic acid for example, and the acid anhydrides of described monocarboxylic acid and ester, for example acrylate or methacrylic ester.
The example of suitable unsaturated fatty acids D is oleic acid, ricinolic acid, linolic acid, linolenic acid, erucic acid, and the lipid acid that derives from soybean, linseed oil, Viscotrol C and Sunflower Receptacle.
Specially suitable carboxylicesters D is methyl methacrylate, hydroxyethyl methylacrylate and Rocryl 410.
Spendable other comonomers D is alcohol, comprise fatty alcohol, for example glyceryl monolaurate, Zerol, ethylene glycol monomethyl ether, polyethylene monomethyl ether, phenylcarbinol, DODECANOL, 1-, 1-tetradecanol, 1-cetyl alcohol, and unsaturated fatty alcohol.
Other suitable comonomer D are acrylate, alkyl acrylate particularly, for example n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, vinylformic acid Lauryl Ester, stearyl acrylate base ester, or acrylic acid hydroxy alkyl ester, for example Hydroxyethyl acrylate, Propylene glycol monoacrylate and vinylformic acid hydroxy butyl ester.Acrylate can a kind of simple especially mode be introduced into polymkeric substance by Michael addition at the amino place of ultrabranching polyamide.
The amount of comonomer D depends on that polymkeric substance treats the degree of modification conventionally.The amount of comonomer D is generally 0.5 % by weight to 40 % by weight, and preferred 1 % by weight to 35 % by weight, based on monomer A used 2and B 3total amount meter.
According to monomer used and amount, and according to reaction conditions, ultrabranching polyamide can have terminal carboxyl(group) (COOH) or terminal amino group (NH, NH 2) or the two all have.Be added for the selection of functionalized comonomer D and conventionally depend on end group and the number of reacting with D.If C-terminal is group modified, to every mole of C-terminal group preferably use 0.5 to 2.5, preferably 0.6 to 2, the amine of 0.7 to 1.5 molar equivalent particularly preferably, for example monoamine or diamines, particularly there is the triamine of primary amino or secondary amino group.
If N-terminal is group modified, to every mole of amino end group preferably use 0.5 to 2.5, preferably 0.6 to 2, the monocarboxylic acid of 0.7 to 1.5 molar equivalent particularly preferably.
As mentioned above, also Michael addition can be used so that N-terminal group and described acrylate reactions, the numerical value of the acrylate molar equivalent using is for this purpose for to be preferably 0.5 to 2.5 with respect to every mole of amino end group, and particularly 0.6 to 2, more preferably 0.7 to 1.5.
Free COOH group number (acid number) in final polyamide products is generally 0 to 400, preferred 0 to 200mgKOH/ gram of polymkeric substance, and it can for example record by titration according to DIN 53240-2.
Monomer A 2conventionally and monomers B 3reaction at elevated temperatures, for example 80 to 180 ℃, particularly 90 to 160 ℃.Preferably at rare gas element for example in nitrogen or vacuum, in the situation that existing or not having solvent, operate, described solvent is water, Isosorbide-5-Nitrae-diox, dimethyl formamide (DMF) or N,N-DIMETHYLACETAMIDE (DMAC) for example.The example of fit closely solvent mixture is the solvent mixture being comprised of water and Isosorbide-5-Nitrae-diox.Yet, must not use solvent; For example, can be using carboxylic acid as initial charge and by its melting, and amine can be added in melt.The water being generated by reaction in polymerization (polycondensation) process for example can vacuum be extracted out, or use suitable solvent for example toluene by component distillation, remove.
Pressure is conventionally inessential, for example, be 1mbar to 100bar absolute pressure.If do not use solvent, the water in reaction simply mode by for example operating under 1 to 500mbar and remove in a vacuum.
Reaction times is generally 5 minutes to 48 hours, and preferably 30 minutes to 24 hours, more preferably 1 hour to 10 hours.
The reaction of carboxylic acid and amine can be carried out in the situation that not existing or having catalyzer.The example of suitable catalyzer is amidation catalyst hereinafter described.
If also use catalyzer, its amount is generally 1 to 5000 ppm by weight, and preferred 10 to 1000 ppm by weight, based on monomer A 2and B 3total amount meter.
During polymerization process or afterwards, if needed, can add described chain extension agent C.In order to carry out the chemical modification of ultrabranching polyamide, can also be before polymerization process, during or add afterwards described comonomer D.
If the reaction of comonomer D needs available conventional amidation catalyst catalysis.The example of described catalyzer is ammonium phosphate, triphenyl phosphite or dicyclohexylcarbodiimide.Particularly, when using heat sensitive comonomer D, and while using methacrylic ester or fatty alcohol as comonomer D, reaction also can be by enzyme catalysis, conventionally 40 to 90 ℃, preferably 50 to 85 ℃, particularly under the existence at free radical inhibitors, operate at 55 to 80 ℃.
And if undesirable crosslinking reaction of radical polymerization and unsaturated functional group is suitable suppressed by operation in rare gas element by inhibitor.The example of described inhibitor is quinhydrones, the monomethyl ether of quinhydrones, thiodiphenylamine, amphyl is 2-tert-butyl-4-methyl-Phenol, the 6-tertiary butyl-2 for example, 4-xylenol, or N-oxygen base (oxyl) compound N-oxygen base-4-hydroxyl-2 for example, 2,6,6-tetramethyl piperidine (hydroxyl-TEMPO), N-oxygen base-4-oxo-2,2,6,6-tetramethyl piperidine (TEMPO), its amount is 50 to 2000 ppm by weight, based on monomer A 2and B 3total amount meter.
Preparation process is preferably with intermittent mode or can be in a continuous manner, in stirred vessel for example, carry out in tubular reactor, in tower reactor or in other popular response devices, the conventional equipment that described reactor can have static state or dynamic mixer and control and operate at rare gas element for pressure-controlling and temperature.
While operating in solvent-free situation, end product directly obtains conventionally, and if necessary, can carry out purifying by conventional purification process.If used solvent, desolventizing can be removed from reaction mixture after reaction by conventional methods, for example, by vacuum distilling.
The feature of the inventive method is easy especially.It makes it possible to prepare ultrabranching polyamide with simple one pot reaction.Without isolated or purified intermediate or intermediate blocking group.Present method is favourable economically, because monomer can be buied and be cheap.
Hyperbranched poly esteramides
Suitable hyperbranched poly esteramides can be by making the carboxylic acid with at least two carboxyls react preparation with the amino alcohols with at least one amino and at least two hydroxyls.
The method originates in and has the carboxylic acid (dicarboxylic acid, tricarboxylic acid or have the more carboxylic acid of high functionality) of at least two carboxyls and have at least one amino alcohol (alkanolamine) amino and at least two hydroxyls.
Suitable carboxylic acid has 2 to 4 conventionally, 2 or 3 carboxyls particularly, and has alkyl, aryl or the arylalkyl containing 1 to 30 C atom.Considered carboxylic acid comprises all dicarboxylic acid, tricarboxylic acid and the tetracarboxylic acid of having stated for ultrabranching polyamide, and these sour derivatives.
The carboxylic acid using is succsinic acid, pentanedioic acid, hexanodioic acid, 1 more preferably, 2-, 1,3-or Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, phthalic acid, m-phthalic acid, terephthalic acid or their dimethyl esters.The utmost point is succsinic acid and hexanodioic acid particularly preferably.
Preferred and suitable amino alcohols (alkanolamine) with at least one amino and at least two hydroxyls are dioxane hydramine and three alkanolamines.The example of operable dioxane hydramine as shown in Equation 1,
Wherein R1, R2, R3 and R4 are hydrogen, C independently of one another 1-6alkyl, C 3-12cycloalkyl or C 6-14aryl (comprising arylalkyl).
The example of suitable dioxane hydramine is diethanolamine, dipropanolamine, diisopropanolamine (DIPA), 2-amino-1, ammediol, 3-amino-1,2-propylene glycol, 2-amino-1,3-propanediol, two butanolamines, two isobutyl hydramine, two (2-hydroxyl-1-butyl) amine, two (2-hydroxyl-1-propyl group) amine and two hexamethylene hydramine.
Three suitable alkanolamines as shown in Equation 2,
Wherein R1, R2 and R3 define suc as formula 1, and l, m and n are the integer of 1-12 independently of one another.Suitable example is as three (methylol) aminomethane.
The amino alcohol using preferably includes diethanolamine (DEA) and diisopropanolamine (DIPA) (DIPA).
In a kind of preferred method, the carboxylic acid using comprises dicarboxylic acid, and the amino alcohol using comprises the alcohol with an amino and two hydroxyls.
The method also can be used for preparing functionalized polyesteramide.For this reason, also use comonomer C, if they can carboxylic acid, amino alcohol and suitable also have monomer M reaction before, during or add afterwards.Produce thus a kind of polymkeric substance by comonomer unit and functional group's chemistry modification thereof.
Therefore, a preferred embodiment of the method is: if carboxylic acid, amino alcohol and suitable also have monomer M reaction before, during or afterwards, also use a kind of comonomer C, produce the polyesteramide of modification.That described comonomer can comprise is a kind of, two kinds or more than Liang Zhong functional group.
Suitable comonomer C be saturated---comprise lipid acid---with undersaturated monocarboxylic acid, its acid anhydrides and ester, alcohol, acrylate, and simple function mentioned above or the more alcohol of high functionality (comprising glycol and polyvalent alcohol), amine (comprising diamines and triamine), and amino alcohol (alkanolamine), as above for as described in hyperbranched polymeric amide.
The amount of comonomer C depends on that polymkeric substance treats the degree of modification conventionally.The amino alcohol of the amount of comonomer C based on used and carboxylic acid monomer's total amount meter are generally 0.5 % by weight to 40 % by weight, preferably 1 % by weight to 35 % by weight.
In final polyesteramide product, the quantity (hydroxyl value) of free OH base is generally 10 to 500, preferably 20 to 450mg KOH/ gram polymkeric substance, can be by for example determining according to the titration of DIN 53240-2.
In final polyesteramide product, the quantity (acid number) of free COOH base is generally 0 to 400, preferably 0 to 200mg KOH/ gram polymkeric substance, and equally can be by determining according to the titration of DIN 53240-2.
Carboxylic acid carries out at elevated temperatures with reacting conventionally of amino alcohol, and for example, at 80-250 ℃, especially 90-220 ℃ carries out at 95-180 ℃.The object of modification if, polymkeric substance reacts with comonomer C, and uses catalyzer (later stage in seeing below) for this reason, and temperature of reaction can regulate according to used catalyzer, operation is carried out conventionally at 90-200 ℃, preferred 100-190 ℃, especially 110-180 ℃.
Operation preferably at rare gas element as nitrogen, or in a vacuum, there is solvent or do not having solvent, as carried out in the situation of Isosorbide-5-Nitrae-dioxs, dimethyl formamide (DMF) or N,N-DIMETHYLACETAMIDE (DMAc).But, to using solvent not require; For example, if can mixing with amino alcohol---being suitably under the existence of catalyzer---, carboxylic acid reacts at elevated temperatures.The water that reaction forms in polymerization (polycondensation) process, for example, absorb or use suitable solvent by component distillation, to remove as toluene in a vacuum.
The reaction terminating of carboxylic acid and amino alcohol conventionally can raising and being discovered suddenly by reaction mixture viscosity rapidly.When viscosity starts to raise, can termination reaction, for example, by cooling termination.Then, the sample of this mixture can be used for determining the quantity of carboxyl in (in advance) polymkeric substance, for example, according to DIN53402-2, by titration, determine to obtain acid number, then, if suitable, can add monomer M and/or comonomer C and react.
Pressure is conventionally unimportant, for example, can be absolute pressure 1mbar to 100bar.If do not use solvent, reaction in water simply method for example, by operating and remove in a vacuum, under absolute pressure 1-500mbar.Reaction times is generally 5 minutes to 48 hours, and preferably 30 minutes to 24 hours, more preferably 1 hour to 10 hours.
As mentioned above, mentioned comonomer C can be before polymerization process, during or add afterwards, to obtain the chemical modification of hyperbranched polyesteramide.
The method can be used a kind of catalysis carboxylic acid to react the catalyzer of (esterification) with amino alcohol.
Suitable catalyzer has an acidic catalyst, preferred organic catalyst, organo-metallic catalyst, or enzyme.
The example of the acid organic catalyst that can mention has sulfuric acid, phosphoric acid, phosphonic acids, Hypophosporous Acid, 50, hydrazine aluminum sulfate, alum, acidic silica gel (pH≤6, especially≤5), and acidic alumina.Other example of spendable acid organic catalyst has general formula Al (OR) 3aluminum compound, and general formula Ti (OR) 4titanate.The example of preferred acid organo-metallic catalyst is selected from dialkyl tin oxide R 2snO, wherein R as above defines.The particularly preferred di-n-butyl stannic oxide that is represented as of acid organo-metallic catalyst, can " oxotin " buy.An example of suitable material is Fascat 4201, it is a kind of di-n-butyl stannic oxide that derives from Atofina.
Preferred acid organic catalyst is to have for example acidic organic compound of phosphate-based, sulfonic group, sulfate group or phosphonate group.Sulfonic acid particularly preferably, as tosic acid.Also can use acid ion exchangers as acid organic catalyst, example is to contain sulfonic group and with the polystyrene resin of the divinyl benzene crosslinked of about 2mol%.
If use catalyzer, it is measured based on carboxylic acid and amino alcohol total amount meter, is generally 1-5000ppm weight, preferably 10-1000ppm weight.
Especially, the reaction of comonomer C also can carry out catalysis by conventional amidation catalyst, conventionally 40-90 ℃, preferably 50-85 ℃, especially at 55-80 ℃, under the existence of free radical inhibitors, carry out.
Method of the present invention can preferably be carried out in mode intermittently, or carry out continuously, for example in stirred vessel, tubular reactor, tower reactor or other popular response device, carry out, reactor can have static state or dynamic mixing tank and conventional pressure-controlling and temperature-control device, and is used in the device operating under rare gas element.
For the operation of not using solvent, final product directly obtains conventionally, and if suitable, can carry out purifying via conventional purification process.If used solvent simultaneously, after reaction, this solvent can common mode be removed from reaction mixture, for example, by vacuum distilling, remove.
Hyperbranched polymkeric substance mentioned above can carry out type of polymerization (polymer-analogous reaction) in addition.Can more effectively regulate its performance thus, thereby make in some cases it be applicable to multiple dispersion.For type of polymerization, the functional group (for example group A or B) that can make to be originally present in polymkeric substance reacts, so that the polymkeric substance of gained contains at least one new functional group.
The type of polymerization of hyperbranched polymer can be carried out during polymkeric substance preparation, carries out immediately, or carry out in independent reactions steps after polyreaction.
If before polymkeric substance is synthetic or during, the component adding also contains other functional group except containing group A and B, product is these other functional groups hyperbranched polymers of stochastic distribution substantially.
For the compound of functional group displacement, first can comprise and treat the new required functional group introducing, thereby and can react with the group B of used hyperbranched polymer raw material the second group of a key of formation.Its example be isocyanate group with hydroxycarboxylic acid or with the reacting of aminocarboxylic acid, to form an acid functionality, or the reacting of OH base and acrylic anhydride, to form a reactive acrylic double bond.
The example of the appropriate functional group that can introduce by suitable reaction compatibility thing comprises, particularly contains the acidity of H atom or the derivative of basic group and these groups, as-OC (O) OR ,-COOH ,-COOR ,-CONHR ,-CONH 2,-OH ,-SH ,-NH 2,-NHR ,-NR 2,-SO 3h ,-SO 3r ,-NHCOOR ,-NHCONH 2,-NHCONHR etc.If suitable, also ionizable functional group can be changed into corresponding salt by suitable acid or alkali.Another kind of possibility is that primary, secondary or tertiary amino is quaternized, for example quaternized with alkylogen or sulfuric acid dialkyl.This step can be used for for example obtaining the hyperbranched polymkeric substance of water miscible or water dispersible.
The R base of described group is preferably alkyl straight or branched, that do not replace or replace.For example, it is C 1-C 30alkyl or C 6-C 14aryl.The example of suitable functional group is-CN or-OR a, R wherein a=H or alkyl.
Hydrophilic and hydrophobic part has specific ratio each other, and for hyperbranched polymer, the application in dispersion is favourable.The hydrophobization of hyperbranched polymer can be by for example using the hydrophobic polymer of simple function to realize, by the hydrophobic polymer of this simple function, the reactive group of existence before polymerization, during or be modified afterwards.Therefore, for example, polymkeric substance of the present invention can be by amine, alcohol, carboxylic acid, epoxide or isocyanate reaction with simple function, saturated or undersaturated aliphatic series or aromatics hydrophobization.
In addition, also can be for example by the difunctionality that contains hydrophobic grouping or more the polyfunctional monomer of high functionality during molecular weight increases, by copolymerization, introduce.For this purpose, can for example use difunctionality or more polyfunctional alcohol, amine, isocyanic ester, carboxylic acid and/or the epoxide of high functionality, they except reactive group also with alkyl, the alkenyl or alkynyl of aromatic group or long-chain.
The example of this monomer is alcohol, as Zerol, glyceryl monooleate, hexylene glycol, ethohexadiol, decanediol, dodecanediol, octadecandiol, dimer fatty alcohol; Amine, as hexamethylene-diamine, octamethylenediamine, dodecane diamines; Isocyanic ester, as aromatics or aliphatic vulcabond and polyisocyanates, as diphenylmethanediisocyanate and more senior oligomer, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, two (two isocyanato-cyclohexyl) methane or two (isocyanato-methyl) hexanaphthene thereof; And acid, as hexanodioic acid, suberic acid, dodecanedioic acid, octadecane diacid or dimer (fatty acid) yl.
Hyperbranched polymkeric substance used according to the invention also can hydrophilization.This can be by for example realizing the hyperbranched polymer that comprises hydroxyl and/or primary amino or secondary amino group by the polymer polyatomic alcohol that changes into high functionality with reacting of oxirane, described oxirane is as oxyethane, propylene oxide, butylene oxide ring or its mixture.For alkoxylate, preferably use oxyethane.But separately also can select functionality is two or higher epoxy alkanol (alkylene oxide alcohol) or epoxy alkanamine (alkylene oxide amine) the synthetic component during as hyperbranched polymer preparation.
Also can generate the hyperbranched polymer with different functionality.This can pass through, for example realizes to carry out functional group's displacement from the mixture reaction of different compounds, or by only making the initial functional group reactions existing of a part realize.
Also can be used for by use ABC type or the AB of polymerization 2c type monomer generates the compound with mixed functionality, the functional group that C representative and A or B do not react under selected reaction conditions.
Polymeric dispersions PD)
Polymeric dispersions PD) use at least one ethylenically unsaturated monomers (M) preparation.Monomer (M) comprises α, β-ethylenically unsaturated monomers, and for the present invention, this unsaturated monomer means the monomer with terminal double link.Monomer (M) is preferably selected from α, the undersaturated monocarboxylic acid of β-ethylenic and dicarboxylic acid and C 1-C 20ester, vinyl aromatic compounds, vinyl alcohol and C that alkanol forms 1-C 30ester, ethylenic unsaturated nitrile, vinyl halide, vinylidene halide, single ethylenic unsaturated carboxylic acid and sulfonic acid, phosphorous-containing monomers, α that monocarboxylic acid forms, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 2-C 30ester, α that alkane glycol forms, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and contain primary amino or the C of secondary amino group 2-C 30acid amides, α that amino alcohol forms, the primary amide of β-ethylenic unsaturated monocarboxylic and N-alkyl derivative and N, N-ethenyl amide compound prodn, allyl alcohol and the C of N-dialkyl derivatives, N-vinyl lactam, open chain 1-C 30ester, α that monocarboxylic acid forms, ester, α that β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and amino alcohol form, acid amides, N that β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and the diamines that contains at least one primary amino or secondary amino group form, N-diallyl amine, N, nitrogen heterocyclic ring, vinyl ether, C that N-diallyl-N-alkylamine, vinyl and allyl group replace 2-C 8-monoolefine, the non-aromatic hydrocarbon with at least two conjugated double bonds, polyethers (methyl) acrylate, containing the monomer of urea groups, and their mixture.
Suitable α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 1-C 20the ester that alkanol forms has (methyl) methyl acrylate, ethylacrylic acid methyl esters, (methyl) ethyl propenoate, ethyl propylene acetoacetic ester, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, ethyl propylene tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, the positive heptyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid 1,1,3,3-tetramethyl-butyl ester, (methyl) EHA, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) vinylformic acid n-undecane base ester, (methyl) tridecyl acrylate, (methyl) vinylformic acid myristin, (methyl) vinylformic acid pentadecyl ester, (methyl) vinylformic acid palm ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid eicosyl ester, (methyl) vinylformic acid docosyl ester, (methyl) vinylformic acid tetracosyl ester, (methyl) vinylformic acid ceryl ester, (methyl) vinylformic acid triacontyl ester, (methyl) vinylformic acid palm oil-base ester, (methyl) vinylformic acid oil base ester, the sub-oil base ester of (methyl) vinylformic acid, (methyl) vinylformic acid flax base ester, (methyl) stearyl acrylate base ester, (methyl) vinylformic acid Lauryl Ester, and their mixture.
Preferred vinyl aromatic compounds has vinylbenzene, 2-methyl styrene, 4-vinyl toluene, 2-(normal-butyl) vinylbenzene, 4-(normal-butyl) vinylbenzene, the positive decyl of 4-() vinylbenzene, and vinylbenzene particularly preferably.
Suitable vinyl alcohol and C 1-C 30the ester that monocarboxylic acid forms has, for example vinyl formate, vinyl-acetic ester, propionate, vinyl butyrate, vinyl laurate, stearic acid vinyl ester, propionate, versatic vinyl acetate, and their mixture.
Suitable ethylenic unsaturated nitrile has vinyl cyanide, methacrylonitrile, and their mixture.
Suitable vinyl halide and vinylidene halide have vinylchlorid, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and their mixture.
Suitable ethylenic unsaturated carboxylic acid, sulfonic acid and phosphonic acids or their derivative have vinylformic acid, methacrylic acid, ethylacrylic acid, α-chloroacrylic acid, β-crotonic acid, toxilic acid, maleic anhydride, methylene-succinic acid, citraconic acid, methylfumaric acid, propene dicarboxylic acid, equisetic acid, fumaric acid, there is 4-10, preferably the monoesters of single ethylenic unsaturated dicarboxylic acid of 4-6 carbon atom is as monomethyl maleate, vinyl sulfonic acid, allyl sulfonic acid, vinylformic acid sulphur ethyl ester, methacrylic acid sulphur ethyl ester, vinylformic acid sulphur propyl ester, methacrylic acid sulphur propyl ester, 2-hydroxyl-3-acryloxy propanesulfonic acid, 2-hydroxy-3-methyl acryloxy propanesulfonic acid, styrene sulfonic acid, with 2-acrylamide-2-methylpro panesulfonic acid.Suitable styrene sulfonic acid and derivative thereof have vinylbenzene-4-sulfonic acid and vinylbenzene-3-sulfonic acid, and their an alkali metal salt or alkaline earth salt, as vinylbenzene-3-sodium sulfonate and vinylbenzene-4-sodium sulfonate.Particularly preferred is vinylformic acid, methacrylic acid and their mixture.
The example of phosphorous-containing monomers for example has vinyl phosphonate and allyl group phosphonic acids.What other was suitable is monoesters and diester, the especially monoesters of phosphonic acids and phosphoric acid and (methyl) vinylformic acid hydroxyalkyl acrylate.Having that other is suitable crossed once by the esterification of (methyl) vinylformic acid hydroxyalkyl acrylate, and also by a kind of different alcohol as alkanol esterification cross phosphonic acids once and the diester of phosphoric acid.The ester that has the independent monomer of following conduct specifically to list for suitable (methyl) vinylformic acid hydroxyalkyl acrylate of these esters is more specifically (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester etc.Corresponding dihydrogen phosphoric acid ester monomer comprises (methyl) vinylformic acid alkyl acid phosphate (phosphoalkyl) ester, as (methyl) vinylformic acid 2-phosphoric acid ethyl ester, (methyl) vinylformic acid 2-phosphoric acid propyl diester, (methyl) vinylformic acid 3-phosphoric acid propyl diester, (methyl) vinylformic acid phosphoric acid butyl ester and (methyl) vinylformic acid 3-phosphoric acid-2-hydroxy-propyl ester.The suitable ester that has phosphonic acids and phosphoric acid and oxyalkylated (methyl) vinylformic acid hydroxyalkyl acrylate to form in addition, example has (methyl) acrylic acid ethylene oxide condensate, as H 2c=C (H, CH 3) COO (CH 2cH 2o) np (OH) 2and H 2c=C (H, CH 3) COO (CH 2cH 2o) np (=O) (OH) 2, wherein n is 1-50.Other is suitable β-crotonic acid alkyl phosphate, toxilic acid alkyl phosphate, fumaric acid alkyl phosphate, (methyl) vinylformic acid phosphate dialkyl ester, β-crotonic acid phosphate dialkyl ester and phosphoric acid allyl ester.The monomer that contains phosphorus group that other is suitable is recorded in WO 99/25780 and US 4,733, and 005(includes in herein by quoting as proof) in.
Suitable α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 2-C 30the ester of alkane glycol has, such as vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, ethylacrylic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, vinylformic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, vinylformic acid 3-hydroxyl butyl ester, methacrylic acid 3-hydroxyl butyl ester, vinylformic acid 4-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester, the own ester of vinylformic acid 6-hydroxyl, the own ester of methacrylic acid 6-hydroxyl, vinylformic acid 3-hydroxyl-2-ethylhexyl, methacrylic acid 3-hydroxyl-2-ethylhexyl etc.
Suitable α, the primary amide of β-ethylenic unsaturated monocarboxylic and N-alkyl and N, N-dialkyl derivatives has acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide, N-n-octyl (methyl) acrylamide, N-(1,1,3,3-tetramethyl butyl) (methyl) acrylamide, N-ethylhexyl (methyl) acrylamide, N-n-nonyl (methyl) acrylamide, the positive decyl of N-(methyl) acrylamide, N-n-undecane base (methyl) acrylamide, N-tridecyl (methyl) acrylamide, N-tetradecyl (methyl) acrylamide, N-pentadecyl (methyl) acrylamide, N-hexadecyl (methyl) acrylamide, N-heptadecyl (methyl) acrylamide, N-nonadecyl (methyl) acrylamide, N-eicosyl (methyl) acrylamide, N-docosyl (methyl) acrylamide, N-tetracosyl (methyl) acrylamide, N-ceryl (methyl) acrylamide, N-triacontyl (methyl) acrylamide, N-palm oil-base (methyl) acrylamide, N-oil base (methyl) acrylamide, sub-oil base (methyl) acrylamide of N-, N-flax base (methyl) acrylamide, N-stearyl (methyl) acrylamide, N-lauryl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, morpholinyl (methyl) acrylamide.
Suitable N-vinyl lactam and derivative thereof have, such as NVP, N-vinyl piperidone, N-caprolactam, N-vinyl-5-N-methyl-2-2-pyrrolidone N-, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-hexanolactam, N-vinyl-7-ethyl-2-hexanolactam etc.
Suitable open chain N-ethenyl amide compound prodn has, for example N-vinyl formamide, N-vinyl-N-METHYLFORMAMIDE, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl propionic acid amide, N-vinyl-N-methyl propanamide and N-vinyl butyramide.
Suitable α, the ester that β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and amino alcohol form has (methyl) vinylformic acid N, N-dimethylamino methyl esters, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid N, N-diethylamino propyl ester and (methyl) vinylformic acid N, N-dimethylamino cyclohexyl.
Suitable α, the acid amides that β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and the diamines that contains at least one primary amino or secondary amino group form has, N-[2-(dimethylamino) ethyl] acrylamide, N-[2-(dimethylamino) ethyl] Methacrylamide, N-[3-(dimethylamino) propyl group] acrylamide, N-[3-(dimethylamino) propyl group] Methacrylamide, N-[4-(dimethylamino) butyl] acrylamide, N-[4-(dimethylamino)-butyl] Methacrylamide, N-[2-(diethylamino) ethyl] acrylamide, N-[4-(dimethylamino) cyclohexyl] acrylamide, N-[4-(dimethylamino) cyclohexyl] Methacrylamide etc.
In addition suitable monomer M) also have N, N-diallyl amine and N, N-diallyl-N-alkylamine and their acid salt, and quaternized products.Alkyl is herein preferably C 1-C 24alkyl.Preferred N, N-diallyl-N-methylamine and N, N-diallyl-N, N-Dimethyl Ammonium compound, as muriate and bromide.
The monomer M that other is suitable) there is the nitrogen heterocyclic ring of vinyl and allyl group replacement as N-vinyl imidazole or N-vinyl-glyoxal ethyline, and the heteroaryl compound of vinyl and allyl group replacement, as 2-vinyl pyridine and 4-vinylpridine, 2-allyl pyridine and 4-allyl pyridine, and their salt.
Suitable C 2-C 8monoolefine has ethene, propylene, iso-butylene, isoprene, divinyl etc. with the non-aromatic hydrocarbon with at least two conjugated double bonds.
Suitable polyethers (methyl) acrylate has the compound of general formula (A),
Wherein
The order of epoxy alkane unit is arbitrarily,
K and l are the integer of a 0-100 independently of one another, and the summation of k and l is at least 3,
R afor hydrogen, C 1-C 30alkyl, C 5-C 8cycloalkyl, C 6-C 14aryl or (C 6-C 14) aryl-(C 1-C 4) alkyl,
R bfor hydrogen or C 1-C 8alkyl,
Y is O or NR c, R wherein cfor hydrogen, C 1-C 30alkyl or C 5-C 8cycloalkyl.
Preferably, k is the integer of a 1-100, is more preferably the integer of the integer of 3-50, especially 4-25.Preferably, l is the integer of a 0-100, is more preferably the integer of the integer of 3-50, especially 4-25.
K and l and be preferably 3-200, especially 4-100.
Preferably, the R in formula (A) afor hydrogen or C 1-C 18alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, n-pentyl, n-hexyl, octyl group, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl.
Preferably, R bfor hydrogen or C 1-C 6alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl or n-hexyl, especially hydrogen, methyl or ethyl.Particularly preferred R bfor hydrogen or methyl.
Preferably, the Y in formula (A) is O or NH, especially O.
The example of suitable polyethers (methyl) acrylate is above-mentioned α, the polycondensation product of β-ethylenic unsaturated monocarboxylic and/or dicarboxylic acid and their acyl chlorides, acid amides and acid anhydrides and Aethoxy Sklerol.Suitable Aethoxy Sklerol can easily pass through oxyethane, 1,2 epoxy prapane and/or Epicholorohydrin and starting molecule, as water or short chain alcohol R athe reaction preparation of-OH.Oxirane can be used alone, alternately uses continuously or use with form of mixtures.Polyether acrylate can be separately or with form of mixtures for the preparation of emulsion polymer used according to the invention.
Polymeric dispersions PD) preferably include at least one polyethers (methyl) acrylate of copolymerized form, it is selected from the compound of general formula I or II or their mixture,
Wherein
N is the integer of a 3-15, the integer of preferred 4-12,
R afor hydrogen, C 1-C 20alkyl, C 5-C 8cycloalkyl or C 6-C 14aryl,
R bfor hydrogen or methyl.
The commercially available acquisition of suitable polyethers (methyl) acrylate, it is called Bisomer for for example name from Laporte Performance Chemicals, the multiple product type of UK.These products comprise, for example Bisomer mPEG 350MA, it is a kind of methoxy poly (ethylene glycol) monomethacrylates (methoxypolyethylene glycol monomethacrylate).
The suitable example containing urea groups monomer is the derivative of N-vinyl urea or N-allyl urea or tetrahydroglyoxaline-2-ketone.They comprise N-vinyl-tetrahydroglyoxaline-2-ketone and N-allyl imidazole quinoline-2-ketone, N-vinyloxy group ethyl imidazol(e) quinoline-2-ketone, N-(2-(methyl) acrylamido ethyl) tetrahydroglyoxaline-2-ketone, N-(2-(methyl) acryloxy ethyl) tetrahydroglyoxaline-2-ketone (being 2-urea groups (methyl) acrylate), N-[2-((methyl) acryloxy acetamido) ethyl] tetrahydroglyoxaline-2-ketone etc.
The monomer that preferably contains urea groups is N-(2-acryloxy ethyl) tetrahydroglyoxaline-2-ketone and N-(2-methacryloxyethyl) tetrahydroglyoxaline-2-ketone.Particularly preferably N-(2-methacryloxyethyl) tetrahydroglyoxaline-2-ketone (2-urea groups methacrylic ester, UMA).
Above-mentioned monomer M) can be used alone, with the form of mixtures with same class monomer, use, or use with the form of mixtures with inhomogeneity monomer.
For letex polymerization, preferably use based on monomer M) gross weight counts at least 40 % by weight, more preferably at least 60 % by weight, are especially at least one monomer M 1 of at least 80 % by weight), it is selected from α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 1-C 20ester, vinyl aromatic compounds, vinyl alcohol and C that alkanol forms 1-C 30ester, ethylenic unsaturated nitrile, vinyl halide, vinylidene halide that monocarboxylic acid forms, and their mixture (principal monomer).Preferably, monomer M 1) for the amount of letex polymerization based on monomer M) gross weight meter is up to 99.9 % by weight, is more preferably up to 99.5 % by weight, is especially up to 99 % by weight.
Principal monomer M1) be preferably selected from:
(methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, the just own ester of (methyl) vinylformic acid, the positive heptyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid n-octyl, (methyl) 2-EHA, vinylbenzene, 2-methyl styrene, vinyl-acetic ester, vinyl cyanide, methacrylonitrile, and their mixture.
Except at least one principal monomer M1), preparation PD) free-radical emulsion polymerization in also can use at least one other monomer M 2), its common content less (secondary monomer).For letex polymerization, preferably using based on monomer M) gross weight meter is up to 60 % by weight, is more preferably up to 40 % by weight, especially be up at least one monomer M 2 of 20 % by weight), it is selected from the acid anhydrides of ethylenic unsaturated monocarboxylic and dicarboxylic acid and ethylenic unsaturated dicarboxylic acid and half ester (halbestern), ethylenic unsaturated sulfonic acid, (methyl) acrylamide, (methyl) vinylformic acid C 1-C 10hydroxyalkyl acrylate, C 1-C 10hydroxyalkyl (methyl) acrylamide, and their mixture.Preferably, monomer M 2) if---existence---for the amount of letex polymerization based on monomer M) gross weight counts at least 0.01 % by weight, more preferably at least 0.05 % by weight, especially at least 0.1 % by weight, particularly at least 0.5 % by weight, more especially at least 1 % by weight.
For letex polymerization, particularly preferably use 0.1 % by weight to 60 % by weight, preferred at least one monomer M 2 of 0.5 % by weight-40 % by weight, especially 1 % by weight-20 % by weight).First kind monomer M 2) comprise that at least one is with the monomer of acid groups, be preferably selected from the unsaturated C of single ethylenic 3-C 8monocarboxylic acid, the unsaturated C of single ethylenic 4-C 8dicarboxylic acid, their acid anhydrides and half ester, single ethylenic unsaturated sulfonic acid and their mixture.The monomer M 2 that contains acid groups) content of (if having this monomer) is based on monomer M) gross weight meter be preferably more preferably 0.1 % by weight-10 % by weight of 0.05 % by weight-15 % by weight.Equations of The Second Kind monomer M 2) comprise single ethylenically unsaturated monomers of at least one neutrality, it is preferably selected from the unsaturated C of single ethylenic 3-C 8the acid amides of monocarboxylic acid, the unsaturated C of single ethylenic 3-C 8hydroxyl-the C of monocarboxylic acid 2-C 4alkyl ester, and their mixture.Neutral monomer M2) content of (if having this monomer) is based on monomer M) gross weight meter be preferably 0.01 % by weight-15 % by weight, 0.1 % by weight-10 % by weight more preferably.The 3rd class monomer M 2) comprise that at least one is with the mixture of the monomer of acid groups and single ethylenically unsaturated monomers of at least one neutrality.These monomer M 2) summation is based on monomer M) gross weight meter be preferably 0.1 % by weight-20 % by weight, 0.5 % by weight-15 % by weight more preferably.Monomer M 2) be especially selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, maleic anhydride, acrylamide, Methacrylamide, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl Methacrylamide, and their mixture.
The example of the combination specially suitable principal monomer M1 for the inventive method) is as follows:
N-butyl acrylate, methyl methacrylate;
N-butyl acrylate, methyl methacrylate, vinylbenzene;
N-butyl acrylate, vinylbenzene;
N-butyl acrylate, EHA;
N-butyl acrylate, EHA, vinylbenzene.
Above-mentioned specially suitable principal monomer M1) combination can with specially suitable monomer M 2) combination, described monomer M 2) be preferably selected from vinylformic acid, methacrylic acid, acrylamide, Methacrylamide and their mixture.
In a specific embodiments, preparation PD) free-radical emulsion polymerization in except M1) and if---existence---M2), also use at least one polyethers (methyl) acrylate to carry out.This polyethers (methyl) acrylate is preferably with based on monomer M) total restatement be no more than 25 % by weight, more preferably no more than the amount of 20 % by weight, use.For letex polymerization, particularly preferably use 0.1 % by weight-20 % by weight, preferred at least one polyethers (methyl) acrylate of 1 % by weight-15 % by weight.Suitable polyethers (methyl) acrylate be mentioned above those.Preferably, polyethers (methyl) acrylate is selected from the compound of general formula I or II or their mixture,
N is the integer of a 3-15, the integer of preferred 4-12,
R afor hydrogen, C 1-C 20alkyl, C 5-C 8cycloalkyl or C 6-C 14aryl,
R bfor hydrogen or methyl.
In a specific embodiment, preparation PD) free-radical emulsion polymerization is except M1) and if---existence---M2) and/or polyethers (methyl) acrylate, use at least one monomer that contains urea groups to carry out.This urea functional monomer is in based on monomer M) gross weight be preferably no more than 25 % by weight, more preferably no more than the amount of 20 % by weight, use.For letex polymerization, particularly preferably use 0.1 % by weight to maximum 20 % by weight, more preferably use at least one monomer that contains urea groups of 1 % by weight-15 % by weight.The suitable monomer that contains urea groups is those that above specifically list.When preparation polymeric dispersions of the present invention, except aforementioned monomer M), also can use at least one linking agent.The monomer with crosslinked function is the compound in molecule with at least two polymerisable, unsaturated unconjugated double bonds of ethylenic.Be cross-linked and also can for example by photochemistry activation, occur.For this purpose, also can use at least one monomer that contains group that can photoactivation with preparation PD).Light trigger also can add in addition.Be cross-linked and also can realize by for example such functional group, this functional group can carry out chemical crosslink reaction with complementary functional group.In this case, two complementary groups all can be connected on emulsion polymer.For being cross-linked, can use a kind of linking agent, it can carry out chemical crosslink reaction with the functional group of emulsion polymer.
Suitable linking agent has, for example acrylate, methacrylic ester, at least allyl ethers or the vinyl ether of dihydroxy alcohol.The hydroxyl of parent alcohol is etherificate or esterification wholly or in part; But linking agent comprises at least two ethylenic unsaturated groups.
The example of parent alcohol has dihydroxy alcohol, as 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butyleneglycol, 1, 3-butyleneglycol, 2, 3-butyleneglycol, 1, 4-butyleneglycol, but-2-ene-1, 4-glycol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexylene glycol, 1, 6-hexylene glycol, 1, 10-decanediol, 1, 2-dodecanediol, 1, 12-dodecanediol, neopentyl glycol, 3-methylpent-1, 5-glycol, 2, 5-dimethyl-1, 3-hexylene glycol, 2, 2, 4-trimethylammonium-1, 3-pentanediol, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol, 1, two (hydroxymethyl) hexanaphthenes of 4-, hydroxy new pentane acid neopentyl glycol monoesters, 2, two (4-hydroxy phenyl) propane of 2-, 2, two [4-(2-hydroxypropyl) phenyl] propane of 2-, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, four propylene glycol, 3-sulfo-pentane-1, 5-glycol, and polyoxyethylene glycol, polypropylene glycol and polytetrahydrofuran, the molecular weight of described polymkeric substance is 200-10000.Except the homopolymer of oxyethane or propylene oxide, also can use the segmented copolymer of oxyethane or propylene oxide, or the multipolymer that contains oxyethane and propylene oxide group.The example having more than the parent alcohol of two hydroxyls has TriMethylolPropane(TMP), glycerine, tetramethylolmethane, 1,2,5-penta triol, 1,2, and 6-hexanetriol, the acid of cyanogen urea, sorbitanic, carbohydrate are as sucrose, glucose and seminose.Certainly also can use with oxyethane or propylene oxide reaction after as the polyhydroxy-alcohol of ethoxylate or propoxylated glycerine accordingly.First polyhydroxy-alcohol also can change into corresponding glycidyl ether by reacting with Epicholorohydrin.
Other suitable linking agent is vinyl ester or monohydroxy unsaturated alcohol and the unsaturated C of ethylenic 3-C 6the ester that carboxylic acid forms, the example of described acid is vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid or fumaric acid.The example of this alcohol has vinyl carbinol, 1-butylene-3-alcohol, 5-hexen-1-ol, 1-OCOL, 9-decen-1-ol, two cyclopentenols (dicyclopentenyl alcohol), 10-undecene-1-ol, styryl carbinol, geraniol, crotyl alcohol or cis-9-vaccenic acid-1-alcohol.Another selection is that the example of described polycarboxylic acid is propanedioic acid, tartrate, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succsinic acid by the polycarboxylic acid esterification of the undersaturated alcohol of monohydroxy.
Other suitable linking agent is the ester of unsaturated carboxylic acid and above-described polyhydroxy-alcohol, and example has the ester of oleic acid, β-crotonic acid, styracin or Shiyixisuan Undecylenic Acid and above-described polyhydroxy-alcohol.
In addition, suitable linking agent is straight or branched, line style or ring-type, aliphatic series or the aromatic hydrocarbon with at least two two keys, for aliphatic hydrocrbon, it must be unconjugated, example is divinylbenzene, divinyl toluene, 1,7-octadiene, 1, the polyhutadiene that 9-decadiene, 4-vinyl-1-tetrahydrobenzene, trivinyl hexanaphthene or molecular weight are 200-20000.
Other suitable linking agent is acrylamide, Methacrylamide and is the N-allyl amine of at least dual functional amine.This amine is, 1，2-diaminoethane, 1 for example, 3-diaminopropanes, 1,4-Diaminobutane, 1,6 diamino hexane, 1,12-dodecane diamines, piperazine, diethylenetriamine or isophorone diamine.The suitable acid amides being formed by allyl amine and unsaturated carboxylic acid in addition, described carboxylic acid is as the carboxylic acid of vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid or at least binary as above.
In addition, triallylamine and triallyl monoalkyl ammonium salt, as triallyl ammonio methacrylate or triallyl methyl the ammonium sulfate also applicable linking agent of doing.
Suitable urea derivatives in addition, the N-vinyl compound of at least dual functional acid amides, cyanurate or carbamate, as the N-vinyl compound of urea, ethylidene-urea, propylidene urea or tartramide (tartaramide), N for example, N '-divinyl ethylidene-urea or N, N '-divinyl propylidene urea.
Other suitable linking agent has divinyl diox, Tetraallylsilane or four vinyl silanes.Should understand the mixture that also can use aforesaid compound.Preferably use water-soluble cross-linker.
In addition, cross-linking monomer also comprises that those also contain the monomer of the reactive functional groups that can react with added linking agent except ethylenic unsaturated double-bond, and described reactive functional groups is as aldehyde radical, ketone group or Oxyranyle.Described functional group is preferably ketone group or aldehyde radical.Ketone group or the aldehyde radical preferably ethylenically unsaturated compounds by can copolymerization and ketone group or aldehyde radical copolymerization are connected to polymkeric substance.Suitable this compound is the vinyl alkyl ketone in propenal, Methylacrylaldehyde, alkyl with individual, preferred 1-10 the carbon atom of 1-20; formyl radical vinylbenzene; in alkyl, there is one or two ketone group or aldehyde radical or there is (methyl) alkyl acrylate of an aldehyde radical and a ketone group; described alkyl preferably includes and amounts to 3-10 carbon atom, and example is as described in DE-A-2722097 (methyl) acryloxyalkyl propionic aldehyde.In addition, suitable N-oxoalkyl group (methyl) acrylamide that also has known class, as known in US-A-4226007, DE-A-2061213 or DE-A-2207209.Particularly preferred is acetoacetyl (methyl) acrylate, acetoacetoxy groups ethyl (methyl) acrylate, is in particular diacetone acrylamide.Linking agent is preferably a kind of compound of---especially two to the five---functional groups that can react with functional group's (especially ketone group or aldehyde radical) of polymkeric substance that have at least two.Be used for comprising with the functional group of ketone group or cross-link, for example hydrazides, azanol or oxime ether or amino.Suitable hydrazides group compound is that for example molecular weight is no more than the poly carboxylic acid hydrazides of 500g/mol.Particularly preferred hydrazide compound is the dicarboxyl acid dihydrazide (dicarboxylic dihydrazide) with a preferred 2-10 carbon atom.Their example comprises careless acid dihydrazide, propanedioic acid two hydrazides, amber acid dihydrazide, pentanedioic acid two hydrazides, adipic dihydrazide, sebacic dihydrazide, Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides and/or isophthalic dihydrazide.Particularly advantageously: adipic dihydrazide, sebacic dihydrazide and isophthalic dihydrazide.The suitable compound with azanol or oxime ether is for for example at those described in WO 93/25588.
By hydrotropisms's polymeric dispersions PD) in suitably add additive (additization), also can produce in addition surface-crosslinked.Adding of this additive comprises, for example, add light trigger or siccative.Suitable light trigger is the light trigger being inspired by the sun, and example has benzophenone or derivatives thereof.Suitable siccative is for recommending the metallic compound for aqueous alkide resin, and they are for example based on Co or Mn(summary: U.Poth, Polyester und Alkydharze, 2005, the 183 pages of Vincentz Network and after).
Crosslinking component is preferably counted 0.0005 % by weight-5 % by weight, the more preferably amount use of 0.001 % by weight-2.5 % by weight, especially 0.01 % by weight-1.5 % by weight with the gross weight (comprising linking agent) of the monomer based on for polymerization.
In a specific embodiment, letex polymerization use the compound based on can polymerization gross weight meter at least 98 % by weight, more preferably single ethylenically unsaturated compounds of at least 99 % by weight, especially at least 99.5 % by weight, particularly 100 % by weight carries out.
A specific embodiment is polymeric dispersions PD) do not comprise the linking agent of copolymerization.
Monomer mixture M) radical polymerization can be carried out under the existence of at least one conditioning agent.The gross weight of the monomer of the usage quantity of conditioning agent based on for polymerization count preferably 0.0005 % by weight-5 % by weight/, more preferably 0.001 % by weight-2.5 % by weight, especially 0.01 % by weight-1.5 % by weight.
Conditioning agent (polymerization regulator) is for having the general name of a compounds of high transfer constant.Conditioning agent accelerating chain shift reaction, so that the polymerization degree of resulting polymers reduces, and can not affect overall reaction rates.Conditioning agent can be divided into simple function, difunctionality or multifunctional conditioning agent according to the number that can cause the functional group of one or more chain transfer reactions in molecule.Suitable conditioning agent is for example described in detail in J.Brandrup by K.C.Berger and G.Brandrup, E.H.Immergut, Polymer Handbook, 3 rded., John Wiley & Sons, New York, in 1989, p.II/81-II/141.
The example of suitable conditioning agent comprises aldehydes, as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde-n and isobutyric aldehyde.
Other spendable conditioning agent is: formic acid and salt thereof or ester, and as ammonium formiate, 2,5-phenylbenzene-1-hexene, sulfovinic acid ammonium and hydroxyl ammonium phosphate.
Other suitable conditioning agent has halogen compounds, and example has alkylogen, as tetrachloromethane, chloroform, bromo-trichloromethane, bromofom, allyl bromide 98 and benzylated title compound, as phenmethyl chlorine or phenmethyl bromine.
Other suitable conditioning agent has allylic cpd, as vinyl carbinol, functionalized allyl ethers, as allyl group ethoxylate, alkyl allyl ethers or allylin.
As conditioning agent, preferably use the compound of the sulphur that contains combining form.
The example of this compounds is inorganic bisulfites, pyrosulfite (disulfite) and hyposulfite; Or organic thioether, disulfide, polythiaether, sulfoxide and sulfone.They comprise di-n-butyl thioether, di-n-octyl thioether, diphenylsulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide ether, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, di-alcohol thioether (diethanol sulfide), di-t-butyl trithioether, dimethyl sulfoxide (DMSO), dialkyl sulfide, dialkyl disulfides ether and/or diaryl sulfide.
Suitable polymerization regulator also comprises mercaptan (compound that contains sulphur with the form of SH base, also referred to as mercaptan).Preferential conditioning agent is simple function, two senses and polyfunctional mercaptan, mercaptoalcohol and/or mercaptan carboxylic acid.The example of these compounds has thioglycol acid allyl ester, thioglycol acetoacetic ester, halfcystine, 2 mercapto ethanol, 1,3-mercaprol, 3-sulfydryl the third-1,2-glycol, 1,4-Mercaptobutanol, Thiovanic acid, 3-thiohydracrylic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid, thiocarbamide and alkyl sulfhydryl, as normal-butyl mercaptan, n-hexyl mercaptan or lauryl mercaptan.
The example of two sense conditioning agents---two sulphur atoms that it comprises combining form---has dual functional thio-alcohol (thiol), as dimercaptopropane sulphonate (sodium salt), dimercaptosuccinic acid(DMSA), dimercapto-1-propyl alcohol, dimercaptoethane, dimercaptopropane, dimercapto butane, dimercapto pentane, dimercapto hexane, ethylene glycol bisthioglycolate (thioglycol acid esters) and butyleneglycol two (thioglycol acid esters).The example of multifunctional conditioning agent has the compound comprising more than the sulphur atom of two combining forms.The example is the mercaptan of trifunctional and four senses.
The use that can be used alone or be bonded to each other of all above-mentioned conditioning agents.A specific embodiment relates to by free-radical emulsion polymerization and adds polymeric dispersions PD prepared by conditioning agent.
For preparing polymkeric substance, can be by the initiator that forms free radical by monomer polymerization.
Initiator as radical polymerization, can adopt conventional peralcohol and/or azo-compound for this object, example has peroxy-disulfuric acid an alkali metal salt or ammonium peroxydisulfate, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, ditertiary butyl peroxide, tert-butyl perbenzoate, cross the PIVALIC ACID CRUDE (25) tert-butyl ester, peroxide-2 ethyl hexanoic acid tert-butyl ester, tert butyl permaleic acid, cumene hydroperoxide, peroxidation diamino acid diisopropyl ester, peroxidation two (toluoyl), didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, t-butylperoxy isobutylate, t-butyl peroxy-acetate, two t-amyl peroxy things, tert-butyl hydroperoxide, Diisopropyl azodicarboxylate, 2, two (2-amidine propane) dihydrochlorides of 2 '-azo or 2-2 '-azo-bis--(2-methyl-butyronitrile).The mixture of these initiators is also applicable.
Also can use reducing/oxidizing (being redox) initiator system as initiator.Redox initiator system by least one, normally inorganic reductive agent and a kind of oxygenant of organic or inorganic form.Oxidation component comprises, the initiator of for example above having specifically noted for letex polymerization.The compound of reduction components comprises, the an alkali metal salt of sulfurous acid for example, as S-WAT, sodium bisulfite, the an alkali metal salt of pyrosulphite is as Sodium Pyrosulfite, the bisulfite adduct of aliphatic aldehyde and ketone is as acetone sodium bisulfite (acetone bisulfite), or reductive agent is as methylol-sulfinic acid and salt or xitix.Redox initiator system can be used together with soluble metal compound, and the metal component of described metallic compound can exist with multiple valence state.Common redox initiator system is, for example xitix/ferrous sulfate (II)/peroxidation sodium pyrosulfate, tert-butyl hydroperoxide/sodium pyrosulfate, tert-butyl hydroperoxide/sodium hydroxymethanesulfinate.Each component---as reduction components---also can be mixture, for example, be the sodium salt of methylol-sulfinic acid and the mixture of sodium pyrosulfate.
The total amount meter of the amount of initiator based on treating polymerization single polymerization monomer is generally 0.1 % by weight-10 % by weight, preferred 0.1 % by weight-5 % by weight.In letex polymerization, also can use two or more different initiators.
Polymeric dispersions PD) preparation is carried out conventionally under the existence of at least one surface active cpd.Can be referring to Houben-Weyl to the detailed description of suitable protective colloid, Methoden der organischen Chemie, XIV/1 volume, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, the 411-420 pages.Suitable emulsifying agent also can be referring to Houben-Weyl, Methoden der organischen Chemie, the 14/1st volume, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, the 192-208 pages.
Suitable emulsifying agent is anionic, cationic and nonionic emulsifier.Preferably use emulsifying agent as surfactant, the relative molecular weight of described emulsifying agent is usually less than the molecular weight of protective colloid.More specifically, proved and only used anionic emulsifier, or to use the combination of at least one anionic emulsifier and at least one nonionic emulsifier be suitable.
Spendable nonionic emulsifier is the nonionic emulsifier of araliphatic or aliphatic series, and example has the monoalkyl phenol of ethoxylation, two alkylphenol and trialkyl phenol (EO degree: 3-50; Alkyl: C 4-C 10), the long-chain alcohol of ethoxylation (EO degree: 3-100; Alkyl: C 8-C 36) and homopolymer and the multipolymer of polyethylene/polypropylene oxides.They can comprise the copolymerization epoxy alkane unit of stochastic distribution or block form.Most suitable has, for example Pluronic PE 6800.Preferably use ethoxylate (the alkyl C of long chain alkanol 1-C 30, average degree of ethoxylation is 5-100), wherein, particularly preferably there is C 12-C 20linear alkyl and average degree of ethoxylation are the long chain alkanol ethoxylate of 10-50; And the monoalkyl phenol of ethoxylation.
The example of suitable anionic emulsifier has alkyl sodium sulfate ester (alkyl: C 8-C 22) an alkali metal salt and ammonium salt, ethoxylation alkanol (EO degree: 2-50; Alkyl: C 12-C 18) and ethoxylated alkylphenol (EO degree: 3-50; Alkyl: C 4-C 9) an alkali metal salt and the ammonium salt of sulfuric acid monoester, alkylsulphonic acid (alkyl: C 12-C 18) an alkali metal salt and ammonium salt and alkyl aryl sulphonic acid (alkyl: C 9-C 18) an alkali metal salt and ammonium salt.Other suitable emulsifying agent can be referring to Houben-Weyl, Methoden der organischen Chemie, XIV/1 volume, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, the 192-208 pages.Similarly, suitable anionic emulsifier has two (phenylbenzimidazole sulfonic acid) ethers and/or its alkali metal salts or ammonium salt, they on one or two aromatic ring with C 4-C 24alkyl.These compounds are by for example US-A-4, and 269,749 is known, and commercially available acquisition, for example, with Dowfax the form of 2A1 (Dow Chemical Company) obtains.
Suitable cationic emulsifier is preferably quaternary ammonium halide, for example trimethylammonium cetyl chloride ammonium, methyl tricapryl ammonium chloride, benzyltriethylammoinium chloride or N-C 6-C 20alkyl pyridine, N-C 6-C 20alkyl morpholine or N-C 6-C 20the quaternary compound of alkyl imidazole, for example N-lauryl chloride pyridine.
The amount meter of the amount of emulsifying agent based on treating polymerization single polymerization monomer is generally approximately 0.01 % by weight-10 % by weight, preferably 0.1 % by weight-5 % by weight.
In addition polymeric dispersions PD) can mix with conventional auxiliary agent and additive.These auxiliary agents and additive comprise, for example pH adjusting agent, reductive agent and SYNTHETIC OPTICAL WHITNER, if an alkali metal salt of methylol-sulfinic acid is (as the Rongalit available from BASF Aktiengesellschaft c), complexing agent, reodorant, spices, taste-additive and viscosity modifier, alcohol for example, as glycerine, methyl alcohol, ethanol, the trimethyl carbinol, glycol etc.These auxiliary agents and additive can be in initial chargings, wherein in a kind of charging, add in polymeric dispersions, or add in polymeric dispersions after polymerization finishes.
Polymerization conventionally 0-150 ℃, preferably 20-100 ℃, more preferably at the temperature of 30-95 ℃, carry out.Polymerization is preferably carried out under barometric point, but carry out polymerization under the pressure raising, is also feasible, for example, under the autogenous pressure of each component for polymerization, carry out.In a suitable embodiment, be aggregated at least one rare gas element, as carried out under the existence of nitrogen or argon gas.
Polymerisation medium can only be comprised of water, or by the compositions of mixtures of water and liquid (as methyl alcohol) that can be miscible with water.Preferably only make water.Letex polymerization can periodical operation or charging method carry out, comprise stage or gradient steps.Preferred feedstock method, wherein a part of polymerization batches or a kind of polymer seeds add as initial charging, and be heated to polymerization temperature and start polymerization, then the remaining polymerization batches (charging of normally separating on two or more spaces, the monomer that wherein one or more comprise pure monomer or emulsification form) by continuous, stage or provide to the zone of convergency with the stack of concentration gradient, maintain polymerization simultaneously.
Those skilled in the art should be interpreted as term " seed polymer " a kind of finely divided polymkeric substance of aqueous polymer dispersions form.The weight average particle diameter of seed polymer (weight average, d 50) be conventionally less than 200nm, usually in the scope of 10-150nm.The monomer composition of seed polymer is conventionally inessential.Be not only mainly most suitable by the synthetic seed polymer of vi-ny l aromatic monomers, especially vinylbenzene (being known as vinylbenzene seed), and mainly by vinylformic acid C 1-C 10alkyl ester and/or methacrylic acid C 1-C 10the synthetic seed polymer of alkyl ester (as the mixture by butyl acrylate and methyl methacrylate) is also most suitable.Except these account for the principal monomer of at least 80 % by weight of seed polymer, especially at least 90 % by weight conventionally, seed polymer also can comprise the monomer of the copolymerized form that is different from above-mentioned these monomers, the monomer especially with the water solubility of increase, example has the neutral monomer that has the monomer of at least one acid functional group and/or have the water solubility of increase.The content of this class monomer is no more than 20 % by weight conventionally, is especially no more than 10 % by weight, and if there is this class monomer, its content is generally 0.1 % by weight-10 % by weight, the total amount meter of the compositing monomer based on seed polymer.
In free radical aqueous emulsion polymerization process, it is known to persons of ordinary skill in the art that initiator adds the mode in aggregation container.They can all be included in initial charging and add in aggregation container, or stage or according to its wear rate, use continuously in the process of free radical aqueous emulsion polymerization.Any situation is all carried out in mode known to persons of ordinary skill in the art according to the chemical property of initiator system and polymerization temperature.Preferably, a part is comprised in initial charging, and remainder is provided in the zone of convergency according to its wear rate.
After converging operationJu Hecaozuo, the dispersion forming in polymerization can be carried out physics or chemical processing.The example of this technology is the known technology that object is to reduce residual monomer, for example: by add the mixture of polymerization starter or two or more polymerization starters at suitable temperature, carry out aftertreatment; By water vapor or ammonia steam, carry out the aftertreatment of polymers soln; Or use rare gas element air lift; Or with oxidising agent or reduction agent treated reaction mixture; Adsorption technology, as by impurity absorption at selected medium, as gac on; Or for example carry out ultrafiltration.
Aqueous polymer dispersions PD) solids content conventionally having is counted 20 % by weight-70 % by weight, preferably 40 % by weight-65 % by weight based on polymeric dispersions (comprising added highly branched polymkeric substance).In a specific embodiment, solids content is at least 50 % by weight, is more particularly at least 55 % by weight, is even more particularly at least 58 % by weight.Based on aqueous polymer dispersions (comprising added highly branched polymkeric substance) meter, at least 60 % by weight, even the solids content of at least 65 % by weight is also feasible.
The second-order transition temperature T of the emulsion polymer existing in polymeric dispersions gpreferably be less than 50 ℃, be more preferably less than 40 ℃, be especially less than 30 ℃.
The aqueous polymer dispersions PD of gained) can itself form use, or use with the form of the mixture that---is generally film-forming polymer---with other polymkeric substance, as the binder composition in water-borne coatings (as paint or varnish mixture).
The present invention also provides a kind of coating of waterborne compositions form, and this waterborne compositions comprises at least one dispersion PD as defined above), it comprises a kind of highly branched polymkeric substance as interpolation.Highly branched polymkeric substance also can add in coating with a kind of form of additive.
Except polymeric dispersions PD), the binder composition of coating also can comprise at least one other film-forming polymer.Comprising, Synolac for example.The example of suitable Synolac has water soluble alkyd resin, and it preferably has the weight-average molecular weight of 5000-40000.In addition, to be greater than 40000, to be greater than especially 100000 Synolac be also suitable to weight-average molecular weight.Synolac is a kind of by the polyester of siccative oil, lipid acid or analogue esterification (U.Poth, Polyester und Alkydharze, Vincentz Network 2005).Suitable water soluble alkyd resin is the Synolac with sufficiently high acid number, and acid number is preferably in the scope of 30-65mg KOH/g.If these Synolac are suitable, can be the partially or completely form of neutralization.Weight-average molecular weight is preferably 8000 to 35000, is more preferably 10000 to 35000.
This class other film-forming polymer, particularly Synolac that use can increase the VOC content of coating are not preferred.Therefore, preferred a kind of like this coating, it comprises at least one dispersion PD) and at least one highly branched polymkeric substance, but do not comprise the film-forming polymer being different from beyond the emulsion polymer existing in this polymeric dispersions.
Binder composition of the present invention is preferably used for water-borne coatings.The form of these coating is, for example uncoloured system (transparent varnish) or painted system.The content of pigment can be described by pigment volume concentration (PVC) (PVC).PVC has described pigment (V p) and weighting agent (V f) volume and cumulative volume---by the base-material (V of dry coating b), the cumulative volume of pigment and weighting agent forms---between ratio, be expressed as per-cent: PVC=(V p+ V f) * 100/ (V p+ V f+ V b).Coating can be divided into based on PVC for example several as follows:
The present invention also provides a kind of coating of waterborne compositions form, and it comprises:
-at least one dispersion PD as defined above), it comprises highly branched polymkeric substance as additive,
If-suitable, at least one mineral filler and/or at least one mineral dye,
If-suitable, the auxiliary agent that at least one is common, and
-water.
Preferred a kind of like this coating, it comprises:
-based on solids content, at least one of 10 % by weight-60 % by weight be polymeric dispersions PD as defined above),
The mineral filler of-10 % by weight-70 % by weight and/or mineral dye,
The conventional auxiliary agent of-0.1 % by weight-20 % by weight, and
-add to the water of 100 % by weight.
PD) content that accounts for above-mentioned coating is based on solid meter, and emulsion polymer and one or more highly branched polymkeric substance, do not comprise water.
The coating of waterborne compositions form of the present invention is used preferably as coating.One embodiment of the invention relate to the coating of transparent varnish form.Another embodiment of the invention comprises the coating of emulsion paint form.Pigmented coating of the present invention is preferably water-based semi-gloss paint or high lac varnish form.
Set forth hereinafter a kind of composition of common emulsion paint form.Emulsion paint comprises 30 % by weight-75 % by weight, the preferred nonvolatile element of 40 % by weight-65 % by weight conventionally.They refer to all the components in addition that dewaters in preparation, are at least for example total amount of base-material, filler, pigment, low voc solvent (boiling point is higher than 220 ℃), softening agent and reagent and additive in polymerization.Its amount is roughly:
The finely divided polymeric dispersions PD of a) 3 % by weight-90 % by weight, especially 10 % by weight-60 % by weight),
B) 0 % by weight-85 % by weight, preferably 5 % by weight-60 % by weight, especially at least one mineral dye of 10 % by weight-50 % by weight,
C) 0 % by weight-85 % by weight, the especially mineral filler of 5 % by weight-60 % by weight, and
D) 0.1 % by weight-40 % by weight, the especially conventional auxiliary agent of 0.5 % by weight-20 % by weight.
Polymeric dispersions of the present invention is more preferably applicable to prepare high gloss emulsion paint.The feature of these paints normally pigment volume concentration (PVC) PVC in the scope of 12%-30%.But polymeric dispersions of the present invention is also particularly suitable for masonry paint or the PVC interior paint among 65-80s of PVC within the scope of 30-65.Pigment volume concentration (PVC) PVC refers to the ratio of the cumulative volume of the pigment and filler cumulative volume that is multiplied by after 100 and pigment, filler and base material polymer; Referring to Ullmann ' s der technischen Chemie, the 4th edition, the 15th volume, the 667th page.
Term " pigment " is widely used for, in text of the present invention, referring to all pigment and filler, and the example is colored pigment, white pigment and mineral filler.They comprise inorganic white pigment, as titanium dioxide (the preferably titanium dioxide of rutile form), barium sulfate, zinc oxide, zinc sulphide, white lead carbonate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, lithopone (zinc sulphide+barium sulfate); Or colored pigment, example has ferric oxide, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, prussian blue or urania green.Except mineral dye, emulsion paint of the present invention also can comprise organic colored pigment, example has sepia, gamboge, cologne earth, toluidine red, p-nitroaniline red, organic yellow, indigo, azoic dyestuff, anthraquinone dye and indigoids dyestuff, and dioxazines, quinacridone, phthalocyanine, isoindolinone, and metal complex pigment.Suitable has gas enclosure in addition to increase the synthetic white pigment of scattering of light, as Rhopaque dispersion.
Suitable filler has, and silico-aluminate for example, as feldspar; Silicate, as kaolin, talcum, mica, magnesite; Alkaline earth metal carbonate, as calcium carbonate, its form is as calcite or chalk, magnesiumcarbonate, rhombspar; Alkaline earth metal sulphate, as calcium sulfate; Silicon-dioxide etc.Yes in coating for finely divided filler preferably.Filler can be used as independent component and uses.But in practice, it is specially suitable that filler mixture has been proved to be, example has calcium carbonate/kaolin and calcium carbonate/talcum.Gloss paint only comprises the filler of a small amount of superfine dispersion conventionally, or does not comprise filler.
Finely divided filler also can be used for increasing opacifying power and/or for saving the use of white pigment.For regulating the degree of depth of opacifying power, color harmony color, preferably use the blend of colored pigment and filler.
As mentioned above, the content of pigment can pass through pigment volume concentration (PVC) (PVC) description.For example, the PVC of gloss paint of the present invention is in the scope of 12%-35%, preferred 15%-30%.
Coating of the present invention (water-borne coatings) is except polymeric dispersions PD) also can comprise at least one highly branched polymkeric substance as additive, and if suitable, also comprise other film-forming polymer and pigment and other auxiliary agent.
Except the emulsifying agent for polymerization, conventional auxiliary agent comprises wetting agent or dispersion agent, as sodium polyphosphate, Rapisol or ammonium polyphosphate; An alkali metal salt of acrylic copolymer or copolymer-maleic anhydride and ammonium salt; Polyphosphonate, as 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid sodium; And the salt of naphthene sulfonic acid, especially its sodium salt.
Other suitable auxiliary agent has flowing regulator, defoamer, biocide and thickening material.Suitable thickening material has, and associative thickener for example, as polyurethane thickener.The amount of thickening material is preferably less than 1 % by weight, is more preferably less than 0.6 % by weight, the solid content meter of coating based.
Thereby paint of the present invention is by preparing component in known manner for the mixing device blend of this object in routine.Find, if by pigment, water with water-based paste prepared by---suitable---auxiliary agent or dispersion is suitable, just polymer base material---is generally to aqueous polymer dispersion---afterwards and mixes with pigment paste or pigment dispersion.
Conventionally, enamel-cover of the present invention is containing 30 % by weight-75 % by weight, the preferred nonvolatile element of 40 % by weight-65 % by weight.They refer to the solid content meter based on paint, and all components of the preparation beyond dewatering is at least the total amount of base-material, pigment and auxiliary agent.Volatile constituent is mainly water.
Suitable paint is high lac varnish.The gloss of paint can be determined by DIN 67530.In this case, coating is with wide being coated on a sheet glass of seam of 240 μ m, and at room temperature dry 72 hours.Sample is inserted in the reflexometer of calibration, and under definite input angle, determines that the light returning is reflected or the degree of scattering.Determined reflectometer value is that of glossiness measures (this value is higher, and glossiness is higher).
The glossiness of high lac varnish is preferably more than 60 under 20 °, and is greater than 80 at 60 °.Reflectometer value is measured at 23 ℃, and the nondimensional parameter report to change with input angle, for example, under 20 °, be 40.
Paint of the present invention can be applied on base material in a conventional manner, such as coating, spraying, dipping, roller coat, blade coating etc.
Preferably, it uses as building coating, for applying buildings or building components.Described base material can be mineral substrates, as bottom ash (render), gypsum, plasterboard, masonry or concrete, timber, wood based material, metal or paper (as wallpaper) or plastics (as PVC).
Preferably, paint is used to the inside of buildings, as interior wall, inside door, panelling, handrail, furniture etc.
The feature of paint of the present invention is easy handling, has good processing characteristics and high covering power.Its pollutant load is low.They have good performance, as high water-repellancy, good wet adhesion (especially also for alkyd varnish), high resistance to blocking, good recoatability, and the good fluidity while applying.The equipment using easily water is clean.
The present invention describes in more detail with reference to following nonrestrictive embodiment.
Embodiment:
I. highly branched polymkeric substance is synthetic
HBP 1: hyperbranched polycarbonates
The flask of a 4L is provided with agitator, gas inlet pipe, internal thermometer and reflux exchanger, the trivalent alcohol that adds wherein 1417.6g diethyl carbonate, 2400.0g to be obtained on average to contain 1.5 propylene oxide units by propoxylation TriMethylolPropane(TMP), and 0.4g salt of wormwood, by this initial charge under atmospheric pressure, follow gentle nitrogen to pass into and be heated to approximately 130 ℃.In the process of polycondensation, due to the generation of the ethanol as condensation product, the temperature of reaction mixture is reduced to 105 ℃ in the process of 4h.When boiling temperature is constant, reflux exchanger is distilled device and replaces, and this water distilling apparatus is comprised of the filling post of 20cm, a descending condenser and a receiving vessel, and ethanol is steamed continuously.When removing 770g overhead product, reaction mixture is cooled to 100 ℃, and is that 85% phosphoric acid neutralizes salt of wormwood by adding 0.5g concentration.Mixture is stirred at 100 ℃ again to 1h.Then use nitrogen about 0.5h of air lift at 140 ℃, the residuum of volatile constituent is removed during this period.Afterwards, cooling and assay products.Hydroxyl value is 421mg KOH/g; By GPC(eluent=DMAC, demarcation=PMMA) definite molecular weight is M n=980g/mol and M w=1450g/mol.
HBP 2: hyperbranched polycarbonates
The flask of a 4L is provided with agitator, gas inlet pipe, internal thermometer and reflux exchanger, the trivalent alcohol that adds wherein 591g diethyl carbonate, 3350g to be obtained on average to contain 12 ethylene oxide units by ethoxylated trimethylolpropane, and 0.5g potassium hydroxide, by this initial charge under atmospheric pressure, follow gentle nitrogen to pass into and be heated to approximately 140 ℃.In the process of polycondensation, due to the generation of the ethanol as condensation product, the temperature of reaction mixture is reduced to 110 ℃ in the process of 4h.When boiling temperature is constant, reflux exchanger is distilled device and replaces, and this water distilling apparatus is comprised of the filling post of 20cm, a descending condenser and a receiving vessel, and ethanol is steamed continuously.When removing 405g overhead product, reaction mixture is cooled to 100 ℃, and is that 85% phosphoric acid neutralizes potassium hydroxide by adding 0.5g concentration.Mixture is stirred at 100 ℃ again to 1h.Then use nitrogen about 0.5h of air lift at 140 ℃, the residuum of volatile constituent is removed during this period.Afterwards, cooling and assay products.Hydroxyl value is 151mg KOH/g; By GPC(eluent=DMAC, demarcation=PMMA) definite molecular weight is M n=2750g/mol and M w=5700g/mol.
HBP 3: hyperbranched polycarbonates
The flask of a 4L is provided with agitator, gas inlet pipe, internal thermometer and reflux exchanger, the trivalent alcohol that adds wherein 1182g diethyl carbonate, 2750g to be obtained on average to contain 3 ethylene oxide units by ethoxylated trimethylolpropane, and 0.4g salt of wormwood, by this initial charge under atmospheric pressure, follow gentle nitrogen to pass into and be heated to approximately 140 ℃.In the process of polycondensation, due to the generation of the ethanol as condensation product, the temperature of reaction mixture is reduced to 110 ℃ in the process of 4h.When boiling temperature is constant, reflux exchanger is distilled device and replaces, and this water distilling apparatus is comprised of the filling post of 20cm, a descending condenser and a receiving vessel, and ethanol is steamed continuously.When removing 828g overhead product, reaction mixture is cooled to 100 ℃, and is that 85% phosphoric acid neutralizes salt of wormwood by adding 0.5g concentration.Mixture is stirred at 100 ℃ again to 1h.Then use nitrogen about 0.5h of air lift at 140 ℃, the residuum of volatile constituent is removed during this period.Afterwards, cooling and assay products.Hydroxyl value is 274mg KOH/g; By GPC(eluent=DMAC, demarcation=PMMA) definite molecular weight is M n=2170g/mol and M w=5400g/mol.
II. the preparation of polymeric dispersions
Embodiment 1: the preparation of dispersion 1
To one, be provided with and in measuring apparatus and thermostatic polymerization container, add following material:
Initial charge:
528.0g water
46.7g solids content is 33% and the median size polystyrene seed dispersion that is 30nm
3.67g concentration is the aqueous solution of 15% Sodium Lauryl Sulphate BP/USP
Afterwards, this initial charge is under agitation heated to 85 ℃.Subsequently, remain at this temperature, the material of 5 % by weight 2 is added, and mixture is stirred 5 minutes.Afterwards material 1 was metered in 180 minutes, remaining material 2 added in 195 minutes simultaneously.
Material 1:
543.2g water
The aqueous solution of the Sodium Lauryl Sulphate BP/USP of 125.4g concentration 15%
458.0g n-butyl acrylate
399.6g methyl methacrylate
165.1g vinylbenzene
22.78g methacrylic acid
21.45g methacrylic acid urea ester (N-(2-methacryloxyethyl) tetrahydroglyoxaline-2-ketone)
33.0g Bisomer MPEG 350MA(is available from the methoxy poly (ethylene glycol) monomethacrylates of Laporte Performance Chemicals UK)
Material 2:
83.6g water
4.4g Sodium persulfate
Adding after end of material 1, add 22g water; Adding after end of material 2, makes polymerization proceed 30 minutes, and makes batch of material neutralization with 7.47g ammoniacal liquor (aqueous solution that concentration is 25%).Afterwards 13.2g hydrogen peroxide (aqueous solution that concentration is 5%) is added, the solution that 0.557g xitix is dissolved in to 4.96g water was metered in 60 minutes.Afterwards, dispersion strainer cooling and by 125 μ m is filtered.Generate thus the dispersion of 2.48kg 46%.
Hyperbranched polymer HBP 1 and HBP 2 are sneaked in dispersion 1 with pure substance form, and it is measured as shown in Tables 3 and 4.
Embodiment 2: the preparation of dispersion 2
To one, be provided with and in measuring apparatus and thermostatic polymerization container, add following material:
584.0g water
56.9g solids content is 33% and the median size polystyrene seed dispersion that is 30nm
4.47g concentration is the aqueous solution of 15% Sodium Lauryl Sulphate BP/USP
Afterwards, this initial charge is under agitation heated to 85 ℃.Subsequently, remain at this temperature, the material of 5 % by weight 2 is added, and mixture is stirred 5 minutes.Afterwards material 1 was metered in 180 minutes, remaining material 2 added in 195 minutes simultaneously.
Material 1:
595.6g water
The aqueous solution of the Sodium Lauryl Sulphate BP/USP of 153.0g concentration 15%
576.3g n-butyl acrylate
529.6g methyl methacrylate
207.6g vinylbenzene
28.59g methacrylic acid
Material 2:
16.1g concentration is the aqueous solution of 5% Sodium persulfate
Adding after end of material 1, add 27g water; Adding after end of material 2, makes polymerization proceed 30 minutes, and makes batch of material neutralization with 9.13g ammoniacal liquor (aqueous solution that concentration is 25%).Afterwards 16.11g hydrogen peroxide (aqueous solution that concentration is 5%) is added, the aqueous ascorbic acid that is 10% by 6.71g concentration was metered in 60 minutes.Afterwards, dispersion strainer cooling and by 125 μ m is filtered.Generate thus the dispersion of 2.85kg 48%.
Hyperbranched polymer HBP 3 is sneaked in dispersion 2 with pure substance form, and its amount is as shown in table 5.
III. performance embodiment
1. the preparation of water-miscible paint
Each component (manufacturers is in Table 1) is metered into the amount shown in table 2 (weight part) and order under the stirring of using toothed disk stirrer.Add after TiO 2 pigment, speed is increased to 2000rpm, and batch of material is disperseed until pigment paste is level and smooth, not containing piece.Then, if needed, be cooled to room temperature, under the speed reducing, added remaining ingredient.The formula base-material for water-borne coatings shown in table 2 does not contain highly branched or hyperbranched polymkeric substance.For the coating that contains hyperbranched polymer of the present invention, the weight content of corresponding base-material raises, and corresponding minimizing water-content compensates thus.
Table 1
Table 2: the formula of water-borne coatings
2. the test of water-miscible paint (coating)
The glossiness of coating is determined according to DIN EN ISO 2813: coating be take to stitch is widely coated on sheet glass as 240 μ m, and at room temperature dry 72 hours.Sample is inserted to the turbidity-glossiness reflexometer (Byk-Gardner, Geretsried) through calibration, read reflexometer in the value of 20 ° of input angles and 60 °, and turbidity.The value of determined reflexometer is that of glossiness measures (this value is higher, and glossiness is higher).
Table 3: to adding hyperbranched polymer HBP1 in acrylate dispersoid 1:
*weight percent based on dispersion solid
Table 4: add hyperbranched polymer HBP2 in acrylate dispersoid 1
*weight percent based on dispersion solid
Along with the content increase of hyperbranched polymer, glossiness increases, and turbidity reduces.
Table 5: add hyperbranched polymer HBP3 in acrylate dispersoid 2

Claims (31)

1. a method of preparing the coating of the glossiness with increase, it by being coated with a kind of water-borne coatings on base material, described water-borne coatings contains a kind of aqueous polymer dispersions PD) and a kind of highly-branched polymers, wherein said highly-branched polymers is hyperbranched polycarbonate, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether), or is the mixture of the hyperbranched polymer that contains at least one hyperbranched polycarbonate, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether); Wherein said hyperbranched polymer has 10% to 95% degree of branching DB; Wherein said polymeric dispersions PD) at least one highly-branched polymers that contains 0.1 % by weight to 15 % by weight, the gross weight meter based on described polymeric dispersions; And wherein said aqueous polymer dispersions PD) by least one ethylenically unsaturated monomers M) free-radical emulsion polymerization obtain.
2. a method of preparing the coating of the glossiness with increase, it by being coated with a kind of water-borne coatings on base material, described water-borne coatings contains a kind of aqueous polymer dispersions PD) and a kind of highly-branched polymers, wherein said highly-branched polymers is hyperbranched polycarbonate, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether), or is the mixture of the hyperbranched polymer that contains at least one hyperbranched polycarbonate, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether); Wherein said hyperbranched polymer has 10% to 95% degree of branching DB; Wherein said polymeric dispersions PD) at least one highly-branched polymers that contains 0.1 % by weight to 15 % by weight, the gross weight meter based on described polymeric dispersions; Wherein said aqueous polymer dispersions PD) by least one ethylenically unsaturated monomers M) free-radical emulsion polymerization obtain; And be wherein applied to described water-borne coatings on described base material contain a kind ofly comprise described highly-branched polymers as the aqueous polymer dispersions PD of additive).
3. claim 1 or 2 method, wherein said hyperbranched polymer has 25% to 90% degree of branching DB.
4. the method for claim 3, wherein said hyperbranched polymer has 30% to 80% degree of branching DB.
5. at least one highly-branched polymers that claim 1 or 2 method, wherein said polymeric dispersions PD) contains 0.5 % by weight to 10 % by weight, the gross weight meter based on described polymeric dispersions.
6. claim 1 or 2 method, wherein said monomer M) be selected from α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 1-C 20the ester of alkanol, vinyl aromatic compounds, vinyl alcohol and C 1-C 30the ester of monocarboxylic acid, ethylenic unsaturated nitrile, vinyl halide, vinylidene halogen, single ethylenic unsaturated carboxylic acid and sulfonic acid, phosphorous-containing monomers, α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 2-C 30the ester of alkane glycol, α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and containing the C of primary amino or secondary amino group 2-C 30the acid amides of amino alcohol, α, the primary amide of β-ethylenic unsaturated monocarboxylic and N-alkyl derivative and N, N-dialkyl derivatives, N-vinyl lactam, open chain N-ethenyl amide compound prodn, vinyl carbinol and C 1-C 30the ester of monocarboxylic acid, α, the ester of β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and amino alcohol, α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and containing acid amides, the N of the diamines of at least one primary amino or secondary amino group, N-diallyl amine, N, the nitrogen heterocyclic, vinyl ether, the C that replace with allyl group of N-diallyl-N-alkylamine, vinyl substituted 2-C 8monoolefine, the non-aromatic hydrocarbon with at least two conjugated double bonds, polyethers (methyl) acrylate, containing the monomer of urea groups, and the mixture of above-mentioned substance.
7. claim 1 or 2 method, wherein at least one monomer M 1 of at least 40 % by weight is used in letex polymerization) carry out, described amount is based on monomer M) gross weight meter, described monomer M 1) be selected from α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 1-C 20the ester of alkanol, vinyl aromatic compounds, vinyl alcohol and C 1-C 30the ester of monocarboxylic acid, ethylenic unsaturated nitrile, vinyl halide, vinylidene halogen, and the mixture of above-mentioned substance.
8. the method for claim 7, wherein monomer M 1 described at least one of at least 60 % by weight is used in letex polymerization) carry out, described amount is based on monomer M) gross weight meter.
9. the method for claim 8, wherein monomer M 1 described at least one of at least 80 % by weight is used in letex polymerization) carry out, described amount is based on monomer M) gross weight meter.
10. the method for claim 7, wherein at least one monomer M 2 of maximum 60 % by weight is also used in letex polymerization) carry out, described amount is based on monomer M) gross weight meter, described monomer M 2) be selected from the acid anhydrides of ethylenic unsaturated monocarboxylic and dicarboxylic acid and ethylenic unsaturated dicarboxylic acid and monoesters, (methyl) acrylamide, (methyl) vinylformic acid C 1-C 10hydroxy alkyl ester, C 1-C 10hydroxyalkyl (methyl) acrylamide, and the mixture of above-mentioned substance.
The method of 11. claims 10, wherein monomer M 2 described at least one of maximum 40 % by weight is also used in letex polymerization) carry out, described amount is based on monomer M) gross weight meter.
The method of 12. claims 11, wherein monomer M 2 described at least one of maximum 20 % by weight is also used in letex polymerization) carry out, described amount is based on monomer M) gross weight meter.
The method of 13. claims 7, wherein letex polymerization is also used at least one polyethers (methyl) acrylate of maximum 25 % by weight to carry out, described amount is based on monomer M) gross weight meter.
The method of 14. claims 13, wherein letex polymerization is also used at least one polyethers (methyl) acrylate of maximum 20 % by weight to carry out, described amount is based on monomer M) gross weight meter.
The method of 15. claims 13, wherein said polyethers (methyl) acrylate is selected from compound or its mixture of general formula I or II
Wherein
N is 3 to 15 integer,
R afor hydrogen, C 1-C 20alkyl, C 5-C 8cycloalkyl or C 6-C 14aryl,
R bfor hydrogen or methyl.
The method of 16. claims 15, wherein n is 4 to 12 integer.
The method of 17. claims 7, at least one monomer containing urea groups that wherein maximum 25 % by weight are also used in letex polymerization carries out, described amount is based on monomer M) gross weight meter.
The method of 18. claims 17, at least one monomer containing urea groups that wherein maximum 20 % by weight are also used in letex polymerization carries out, described amount is based on monomer M) gross weight meter.
The coating of 19. 1 kinds of waterborne compositions forms, it comprises:
The dispersion PD of-at least one claim 1 definition), the highly-branched polymers of claim 1 definition of the amount that it comprises a kind of claim 1 definition is as additive,
-optionally, at least one mineral filler and/or at least one mineral dye,
-optionally, conventional auxiliary agent, and
-water.
The coating of 20. claims 19, its form that is transparent varnish.
The coating of 21. claims 19, its form that is emulsion paint.
The coating of 22. claims 21, it comprises:
At least one of-10 % by weight to 60 % by weight comprises a kind of highly-branched polymers as the dispersion PD of additive),
The mineral filler of-10 % by weight to 70 % by weight and/or mineral dye,
The conventional auxiliary agent of-0.1 % by weight to 20 % by weight, and
-add to the water of 100 % by weight.
23. claims 21 or 22 coating, it is the form of water-based semi-gloss paint or high lac varnish.
The coating of 24. claims 21, it is greater than 60 high lac varnish for glossiness when 20 ° of input angles.
The coating of 25. claims 21, it is greater than 80 high lac varnish for glossiness when 60 ° of input angles.
The coating of 26. claims 21, it is the high lac varnish of PVC in 12 to 35 scope.
The coating of 27. claims 26, it is the high lac varnish of PVC in 15 to 30 scope.
The defined highly-branched polymers of 28. claim 1 is the purposes for increasing the glossiness of the coating being generated by this coating as the additive of the defined water-borne coatings of claim 1, and described water-borne coatings contains the defined aqueous polymer dispersions PD of a kind of claim 1).
29. contain the defined aqueous polymer dispersions PD of claim 1 as the highly-branched polymers of any one definition in the claim 1-4 of additive) as the purposes of a kind of component of high lac varnish.
Defined at least one highly-branched polymers of 30. claims 1 is the purposes for increasing the glossiness of the coating being generated by this coating as the additive of the defined coating of claim 1, described coating contains a kind of α based on any one definition at least one claim 6-18, β-ethylenically unsaturated monomers M) emulsion polymer.
The purposes of 31. claims 30, as the additive of paint.
CN200880116779.6A 2007-11-19 2008-11-19 Use of highly branched polymers in polymer dispersions for gloss colours Expired - Fee Related CN101868509B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP07121034.8 2007-11-19
EP07121034 2007-11-19
EP07150041 2007-12-14
EP07150041.7 2007-12-14
PCT/EP2008/065861 WO2009065868A1 (en) 2007-11-19 2008-11-19 Use of highly branched polymers in polymer dispersions for gloss colours

Publications (2)

Publication Number Publication Date
CN101868509A CN101868509A (en) 2010-10-20
CN101868509B true CN101868509B (en) 2014-09-10

Family

ID=40298673

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200880116779.6A Expired - Fee Related CN101868509B (en) 2007-11-19 2008-11-19 Use of highly branched polymers in polymer dispersions for gloss colours

Country Status (10)

Country Link
US (1) US8399554B2 (en)
EP (1) EP2225337B1 (en)
JP (1) JP5591116B2 (en)
CN (1) CN101868509B (en)
AU (1) AU2008327943B2 (en)
ES (1) ES2648799T3 (en)
NO (1) NO2225337T3 (en)
PL (1) PL2225337T3 (en)
PT (1) PT2225337T (en)
WO (1) WO2009065868A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9222015B2 (en) * 2009-11-24 2015-12-29 Swift River Properties, Llc Thermochromic coating and method of manufacturing thereof
WO2011101395A1 (en) * 2010-02-18 2011-08-25 Basf Se Polymer dispersion comprising a highly branched polycarbonate with unsaturated fatty acid groups
AT12285U1 (en) 2010-08-31 2012-03-15 Senoplast Klepsch & Co Gmbh MULTILAYER BODIES COMPRISING A SUBSTRATE AND A PLASTIC SURFACE
WO2012121379A1 (en) * 2011-03-09 2012-09-13 積水化学工業株式会社 Spacer for liquid crystal display element, spacer fluid dispersion for liquid crystal display element, and liquid crystal display element
WO2012138870A1 (en) 2011-04-06 2012-10-11 Stepan Company Multi-arm hydrophilic urethane polymers, methods of making them, and compositions and processes employing them
US20130095999A1 (en) * 2011-10-13 2013-04-18 Georgia Tech Research Corporation Methods of making the supported polyamines and structures including supported polyamines
US9567484B2 (en) * 2012-07-06 2017-02-14 Basf Se Use of aqueous hybrid binders and alkyd systems for coating agents
CN104449181A (en) * 2014-12-22 2015-03-25 常熟市金蝙蝠工艺家具有限公司 Novel paraffin for redwood furniture
KR102158663B1 (en) 2015-12-09 2020-09-22 바스프 코팅스 게엠베하 Carboxy-functional polyether-based reaction product and aqueous basecoat containing the reaction product
CN107523155A (en) * 2016-06-21 2017-12-29 立邦涂料（中国）有限公司 A kind of water-soluble polymer antifreeze
RU2759334C2 (en) 2016-09-21 2021-11-12 Нексткьюр, Инк. Antibodies against siglec-15 and their application methods
US10053533B1 (en) 2017-04-13 2018-08-21 Presidium Usa, Inc. Oligomeric polyol compositions
CN109925589B (en) * 2019-03-05 2021-09-21 江苏长寿棒科技有限公司 Novel prostate expands and splits pipe
WO2021108507A1 (en) * 2019-11-27 2021-06-03 Swimc Llc Low voc coatings including hyper-branched alkylated polymers
JP7014990B1 (en) 2021-03-29 2022-02-15 藤倉化成株式会社 Copolymer, its production method, and coating composition
CN114907552A (en) * 2022-05-25 2022-08-16 广东润昌南星新材料有限公司 Hyperbranched alkyd resin and preparation method and application thereof
CN116144137B (en) * 2023-03-14 2023-07-14 绍兴君合新材料科技有限公司 Preparation method of hyperbranched polyurethane amide toughened ABS plastic

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362427A (en) * 2000-12-29 2002-08-07 国家淀粉及化学投资控股公司 Star-type polymer glue stabilizer
CN1816568A (en) * 2003-07-01 2006-08-09 赛拉尼斯乳胶诺登股份公司 Method for production of a waterborne copolymer dispersion

Family Cites Families (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1329126A (en) 1969-12-11 1973-09-05 Mitsubishi Rayon Co Acrylic fibre and a method for manufacturing the same
JPS5033767B1 (en) 1971-03-11 1975-11-04
DE2722097C3 (en) 1977-05-16 1981-09-17 Basf Ag, 6700 Ludwigshafen (Meth) acryloxy-alkylpropanals, process for their preparation and use thereof
US4226007A (en) * 1979-03-16 1980-10-07 Signode Corporation Sealless strap connection
US4269749A (en) * 1979-04-30 1981-05-26 The Dow Chemical Company Method of imparting salt and/or mechanical stability to aqueous polymer microsuspensions
US4733005A (en) * 1986-04-21 1988-03-22 The Dow Chemical Company Phosphinyl-containing ethylenically unsaturated compounds
US5159047A (en) * 1991-06-14 1992-10-27 E. I. Du Pont De Nemours And Company Coatings containing caprolactone oligomer polyols
DE4219384A1 (en) 1992-06-13 1993-12-23 Basf Ag Dispersion or solution which can be crosslinked at room temperature with hydroxylamines or oxime ethers
DE19524045A1 (en) 1995-07-01 1997-01-02 Basf Ag Highly functionalized polyurethanes
US5786429A (en) 1996-04-18 1998-07-28 Hercules Incorporated Highly branched polyamidoamines and their preparation
JPH10231452A (en) * 1997-02-18 1998-09-02 Dainippon Ink & Chem Inc Method for protecting alkaline inorganic cured item by coating
GB9711625D0 (en) * 1997-06-06 1997-07-30 Ciba Geigy Ag Pigment compositions
NL1007186C2 (en) 1997-10-01 1999-04-07 Dsm Nv ß-hydroxyalkylamide group-containing condensation polymer.
DE19750618A1 (en) 1997-11-14 1999-05-20 Basf Ag Pigment preparation for dispersion dye
US6150468A (en) * 1998-11-12 2000-11-21 National Starch And Chemical Investment Holding Corporation Water soluble amphiphilic heteratom star polymers and their use as emulsion stabilizers in emulsion polymerization
GB9824932D0 (en) 1998-11-16 1999-01-06 Ici Ltd Coating composition
JP4493746B2 (en) * 1998-11-30 2010-06-30 東レ・ダウコーニング株式会社 Coating material
DE19947631A1 (en) 1998-12-22 2000-06-29 Bayer Ag Process for the preparation of highly branched polyols based on glycidol
DE19904444A1 (en) 1999-02-04 2000-08-10 Basf Ag Dendrimers and highly branched polyurethanes
SE514207C2 (en) 1999-03-23 2001-01-22 Perstorp Ab Hyperbranched dendritic polyether and process for its preparation
US6534590B1 (en) * 1999-10-29 2003-03-18 Dow Corning Toray Silicone Co., Ltd. Silicone-grafted vinyl copolymer emulsion composition
US6569956B1 (en) 1999-12-22 2003-05-27 Basf Corporation Hyperbranched polyol macromolecule, method of making same, and coating composition including same
DE10013187A1 (en) 2000-03-17 2001-10-11 Basf Ag Highly functional polyisocyanates
WO2001081441A1 (en) * 2000-04-20 2001-11-01 Akzo Nobel N.V. Branched hydroxyl-functional polyester resin and its use in aqueous cross-linkable binder compositions
AU2000251762A1 (en) * 2000-06-02 2001-12-24 National Starch And Chemical Investment Holding Corporation Water soluble ampiphilic heteratom star polymers and their use as emulsion stabilizers in emulsion polymerization
DE10030869A1 (en) 2000-06-23 2002-01-03 Basf Ag Multifunctional polyisocyanate polyaddition products
US6534600B2 (en) * 2001-03-26 2003-03-18 Michigan Molecular Institute Hyperbranched polyureas, polyurethanes, polyamidoamines, polyamides and polyesters
DE10116767A1 (en) * 2001-04-04 2002-10-10 Basf Ag New polymeric dispersing additives with hyperbranched structures
DE10138216A1 (en) 2001-08-03 2003-02-20 Bayer Ag Production of aliphatic polycarbonate polymer e.g. poly(ether-carbonate) polyol, involves ring-opening polymerization of cyclic carbonate in the presence of double metal cyanide catalyst
DE10147712A1 (en) 2001-09-27 2003-04-17 Basf Ag Process for the production of aliphatic polycarbonates
DE10163163A1 (en) 2001-12-20 2003-07-03 Basf Ag Process for the production of highly functional, hyperbranched polyester by enzymatic esterification
SE524461C2 (en) 2002-01-25 2004-08-10 Perstorp Specialty Chem Ab Chain extended dendritic polyether, composition and use thereof
DE10204979A1 (en) 2002-02-06 2003-08-14 Basf Ag Process for the production of highly functional highly branched polyureas
DE10211664A1 (en) 2002-03-15 2003-10-02 Hyperpolymers Gmbh Preparation of highly branched polyols based on glycosides useful as an additive in paints and adhesives, additive and crosslinker in polymers, in cosmetics, preparation of nano particles and active substance carrier
DE10219508A1 (en) 2002-04-30 2003-11-13 Basf Ag Process for the production of highly functional, hyperbranched polyester
SE524961C2 (en) 2002-08-16 2004-11-02 Celanese Emulsions Norden Ab Waterborne copolymer dispersion and its use in coatings
SE525758C2 (en) * 2002-08-16 2005-04-19 Perstorp Specialty Chem Ab Waterborne homo- or copolymer dispersion, process for its preparation and its use in adhesives for its preparation and its use in adhesives for surface coatings
DE10240817A1 (en) 2002-08-30 2004-03-11 Basf Ag Process for the production of hyperbranched, water-soluble polyester
SE524568C2 (en) * 2002-10-25 2004-08-31 Perstorp Specialty Chem Ab Air-drying water-borne resin composition, process for preparing an air-drying water-borne resin composition and using an amphiphilic air-drying dendritic polymer
SE524960C2 (en) * 2003-02-12 2004-11-02 Celanese Emulsions Norden Ab Polymerization process at elevated pressure in the presence of dendritic polymer
DE10331770A1 (en) 2003-07-11 2005-02-03 Basf Ag Process for the preparation of hyperbranched polymers
US7034072B2 (en) * 2003-07-22 2006-04-25 E. I. Dupont De Nemours And Company Aqueous coating composition
JP4413226B2 (en) 2003-09-12 2010-02-10 ビーエーエスエフ ソシエタス・ヨーロピア Highly branched or hyperbranched highly functional polycarbonate, method for producing and using the same
DE10351401A1 (en) 2003-11-04 2005-06-09 Basf Ag Highly functional, highly branched polyureas
JP2005179511A (en) * 2003-12-19 2005-07-07 Dainippon Ink & Chem Inc Radically polymerizable coating material composition
DE102004006304A1 (en) 2004-02-09 2005-08-25 Basf Ag Highly functional, highly branched polyureas
DE102004039101A1 (en) 2004-08-11 2006-02-23 Basf Ag Process for the preparation of hyperbranched polyamides
DE102004046508A1 (en) * 2004-09-23 2006-03-30 Basf Ag Water-dispersible, high-functionality polyisocyanates
EP2308460A1 (en) 2005-02-21 2011-04-13 Basf Se Composition comprising active agents and at least one nitrogen-containing hyper-branched polymer
DE102005009166A1 (en) * 2005-02-25 2006-08-31 Basf Ag Use of high-functional, hyper branched polycarbonate (obtained by preparing condensation products either by reacting organic carbonates with an aliphatic, aliphatic/aromatic or aromatic alcohol), as solvent auxilary agent
US20060217485A1 (en) * 2005-03-23 2006-09-28 Basf Corporation Pigment dispersant, method of making coating compositions, and coating compositions
DE102005049402A1 (en) * 2005-10-13 2007-04-19 Basf Ag Aqueous binder composition
DE102005056591A1 (en) * 2005-11-25 2007-05-31 Basf Ag Aqueous coating material, especially latex paint for various substrates, contains acrylate-based binder with hydroxyl-functional comonomer, plus pigments, other additives and little or no frost-protection agent
DE102005056592A1 (en) * 2005-11-25 2007-05-31 Basf Ag Novel uncrosslinked, hyperbranched polylysines useful as e.g. adhesive aids, thixotropic agents or phase transfer agents are obtained by catalytic reaction of a salt of lysine with an acid and optionally with comonomers
DE102005060783A1 (en) * 2005-12-16 2007-06-28 Basf Ag Highly functional, hyperbranched polymers and a process for their preparation
US20090061171A1 (en) * 2006-03-22 2009-03-05 Basf Se Substrates coated with branched polyurethanes for electrophotographic printing processes
CN101431985A (en) * 2006-04-28 2009-05-13 巴斯夫欧洲公司 Method for solubilising hydrophobic active substances in an aqueous medium
RU2008150054A (en) * 2006-05-19 2010-06-27 Басф Коатингс Аг (De) POWDER PAINT AND COATINGS WITH HIGH-FUNCTIONAL, HIGH-BRANCHED OR HYPER-BRANCHED POLYCARBONATES
KR20090019858A (en) * 2006-05-23 2009-02-25 바스프 에스이 Use of hyperbranched polycarbonates as a dispersing agent for pigments
KR20090032042A (en) * 2006-06-08 2009-03-31 바스프 에스이 Composite materials on the basis of polyurethanes with improved adhesion
ES2611591T3 (en) * 2006-07-20 2017-05-09 Basf Se Water-based varnishes with highly functional, highly branched or hyperbranched polycarbonates
BRPI0715474A2 (en) * 2006-07-26 2012-02-28 Basf Se HYPER-RAMIFIED POLYCARBONATE, PROCESSES FOR PREPARING HYPER-RAMIFIED POLYCARBONATES, THERMOPLASTIC OR THERMO-RIGID AND POLYOXYMETHYLENE, AND USE OF ONE OR MORE HYPER-RAMIFIED POLYCARBONATES
JP5192673B2 (en) * 2006-08-30 2013-05-08 大日精化工業株式会社 Aqueous pigment dispersion and article using the same
US20100048813A1 (en) * 2006-11-14 2010-02-25 Basf Se Highly-branched or hyper-branched polyester and the production and application thereof
US20090318607A1 (en) * 2006-11-15 2009-12-24 Basf Se Layer materials with improved adhesion comprising elastic polyurethane binder and plastics granules
JP2010512439A (en) * 2006-12-11 2010-04-22 ビーエーエスエフ ソシエタス・ヨーロピア High elastic polyurethane foam
US8314178B2 (en) * 2006-12-15 2012-11-20 Basf Se Polymer dispersions containing highly branched polycarbonates
BRPI0720198A2 (en) * 2006-12-15 2013-12-31 Basf Se WATER POLYMER DISPERSION, PROCESS FOR PREPARING WATER POLYMER DISPERSIONS, USE OF WATER POLYMER DISPERSION, PAPER STRIP, AND PAPER OR PAPER.
MY146993A (en) * 2006-12-19 2012-10-15 Basf Se Thermoplastic moulding compositions having improved ductility
US20100105943A1 (en) * 2007-03-22 2010-04-29 Basf Se Hyperbranched polyesters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362427A (en) * 2000-12-29 2002-08-07 国家淀粉及化学投资控股公司 Star-type polymer glue stabilizer
CN1816568A (en) * 2003-07-01 2006-08-09 赛拉尼斯乳胶诺登股份公司 Method for production of a waterborne copolymer dispersion

Also Published As

Publication number Publication date
EP2225337A1 (en) 2010-09-08
NO2225337T3 (en) 2018-01-20
PT2225337T (en) 2017-11-27
CN101868509A (en) 2010-10-20
WO2009065868A1 (en) 2009-05-28
ES2648799T3 (en) 2018-01-08
EP2225337B1 (en) 2017-08-23
JP5591116B2 (en) 2014-09-17
AU2008327943B2 (en) 2014-01-09
US20100267886A1 (en) 2010-10-21
AU2008327943A1 (en) 2009-05-28
US8399554B2 (en) 2013-03-19
JP2011503337A (en) 2011-01-27
PL2225337T3 (en) 2018-01-31

Similar Documents

Publication Publication Date Title
CN101868509B (en) Use of highly branched polymers in polymer dispersions for gloss colours
CN101910207B (en) Use of highly-branched polymers for producing polymer dispersions with improved freeze/thaw stability
JP5279722B2 (en) Polymer dispersion containing highly branched polycarbonate
CN101605852B (en) Polymer dispersions containing highly branched polycarbonates
US9683126B2 (en) Polymer dispersants
RU2677334C1 (en) Aqueous coating composition and production of multilayer paint systems using said coating composition
CN102131764A (en) Functionalized (meth)acrylate monomer, polymer, coating agent, and production and cross-linking method
EP3024874B1 (en) Novel polymers and use of these as dispersants
CN102844354B (en) Polymer dispersion comprising highly branched polycarbonate with unsaturated fatty acid groups
EP3215558B1 (en) Novel polymer compositions and use of these polymer compositions as dispersants
EP3234033A1 (en) Novel polymer compositions and use of these polymer compositions as viscosity modifiers

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140910

Termination date: 20191119